\n

\n \n 2022\n \n \n (4)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Direct Synthesis of α-Aryl-α-Trifluoromethyl Alcohols via Nickel Catalyzed Cross-Electrophile Coupling.\n \n \n \n\n\n \n Lombardi, L.; Cerveri, A.; Giovanelli, R.; Castiñeira Reis, M.; Silva López, C.; Bertuzzi, G.; and Bandini, M.\n\n\n \n\n\n\n Angewandte Chemie International Edition, 61(47): e202211732. 2022.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

\n

@article{https://doi.org/10.1002/anie.202211732,\nauthor = {Lombardi, Lorenzo and Cerveri, Alessandro and Giovanelli, Riccardo and Castiñeira Reis, Marta and Silva López, Carlos and Bertuzzi, Giulio and Bandini, Marco},\ntitle = {Direct Synthesis of α-Aryl-α-Trifluoromethyl Alcohols via Nickel Catalyzed Cross-Electrophile Coupling},\njournal = {Angewandte Chemie International Edition},\nvolume = {61},\nnumber = {47},\npages = {e202211732},\nkeywords = {Cross-Electrophile Coupling, DFT Calculation, Hydrogen Atom Transfer, Nickel Catalysis, Trifluoromethylation},\ndoi = {https://doi.org/10.1002/anie.202211732},\nabstract = {Abstract A nickel-catalyzed reductive cross-electrophile coupling between the redox-active N-trifluoroethoxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 \\%) and with large functional group tolerance (30 examples). A combined computational and experimental investigation revealed a pivotal solvent assisted 1,2-Hydrogen Atom Transfer (HAT) process to generate a nucleophilic α-hydroxy-α-trifluoromethyl C-centered radical for the Csp2−Csp3 bond forming process.},\nyear = {2022}\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n On the mechanism of the dyotropic expansion of hydrindanes into decalins.\n \n \n \n\n\n \n Santalla, H.; Nieto Faza, O.; Gómez, G.; Fall, Y.; and López, C.\n\n\n \n\n\n\n Organic and Biomolecular Chemistry, 20(5): 1073-1079. 2022.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Santalla20221073,\nauthor={Santalla, H. and Nieto Faza, O. and Gómez, G. and Fall, Y. and López, C.S.},\ntitle={On the mechanism of the dyotropic expansion of hydrindanes into decalins},\njournal={Organic and Biomolecular Chemistry},\nyear={2022},\nvolume={20},\nnumber={5},\npages={1073-1079},\ndoi={https://doi.org/10.1039/D1OB02150H},\n}\n\n

\n

\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Accessible triplet excited states in the photoisomerization of allenes with extended conjugation.\n \n \n \n\n\n \n Alvarez-García, J.; García-Lago, R.; Alonso-Gómez, J.; López, C.; and Cid, M.\n\n\n \n\n\n\n Dalton Transactions, 51(4): 1357-1363. 2022.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Alvarez-Garcia20221357,\nauthor={Alvarez-García, J. and García-Lago, R. and Alonso-Gómez, J.L. and López, C.S. and Cid, M.M.},\ntitle={Accessible triplet excited states in the photoisomerization of allenes with extended conjugation},\njournal={Dalton Transactions},\nyear={2022},\nvolume={51},\nnumber={4},\npages={1357-1363},\ndoi = {https://doi.org/10.1039/D1DT03688B},\n}\n\n

\n

\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n On the mechanism of the Au(I)-mediated addition of alkynes to anthranils to furnish 7-acylindoles.\n \n \n \n\n\n \n Stylianakis, I.; Litinas, I.; Nieto Faza, O.; Kolocouris, A.; and Silva López, C.\n\n\n \n\n\n\n Journal of Physical Organic Chemistry. 2022.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n \n \n 2 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Stylianakis2022,\nauthor={Stylianakis, I. and Litinas, I. and Nieto Faza, O. and Kolocouris, A. and Silva López, C.},\ntitle={On the mechanism of the Au(I)-mediated addition of alkynes to anthranils to furnish 7-acylindoles},\njournal={Journal of Physical Organic Chemistry},\nyear={2022},\ndoi = {https://doi.org/10.1002/poc.4333},\n}\n\n

\n

\n\n\n\n

\n\n\n\n\n\n

\n

\n \n 2021\n \n \n (2)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n The new pharmacological chaperones pbxs increase $α$-galactosidase a activity in fabry disease cellular models.\n \n \n \n\n\n \n Besada, P.; Gallardo-Gómez, M.; Pérez-Márquez, T.; Patiño-álvarez, L.; Pantano, S.; Silva-López, C.; Terán, C.; Arevalo-Goméz, A.; Ruz-Zafra, A.; Fernández-Martín, J.; and Ortolano, S.\n\n\n \n\n\n\n Biomolecules, 11(12). 2021.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Besada2021,\nauthor={Besada, P. and Gallardo-Gómez, M. and Pérez-Márquez, T. and Patiño-álvarez, L. and Pantano, S. and Silva-López, C. and Terán, C. and Arevalo-Goméz, A. and Ruz-Zafra, A. and Fernández-Martín, J. and Ortolano, S.},\ntitle={The new pharmacological chaperones pbxs increase $\\alpha$-galactosidase a activity in fabry disease cellular models},\njournal={Biomolecules},\nyear={2021},\nvolume={11},\nnumber={12},\nart_number={1856},\ndoi = {https://doi.org/10.3390/biom11121856},\n}\n\n

\n

\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Enantioselective CO2 Fixation Via a Heck-Coupling/Carboxylation Cascade Catalyzed by Nickel.\n \n \n \n\n\n \n Cerveri, A.; Giovanelli, R.; Sella, D.; Pedrazzani, R.; Monari, M.; Nieto Faza, O.; López, C. S.; and Bandini, M.\n\n\n \n\n\n\n Chemistry – A European Journal, 27(28): 7657-7662. 2021.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 9 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n \n \n \n \n \n \n \n \n \n \n\n\n\n

\n

@article{Cerveri20217657,\nauthor = {Cerveri, Alessandro and Giovanelli, Riccardo and Sella, Davide and Pedrazzani, Riccardo and Monari, Magda and Nieto Faza, Olalla and López, Carlos Silva and Bandini, Marco},\ntitle = {Enantioselective CO2 Fixation Via a Heck-Coupling/Carboxylation Cascade Catalyzed by Nickel},\njournal = {Chemistry – A European Journal},\nvolume = {27},\nnumber = {28},\npages = {7657-7662},\nkeywords = {asymmetric catalysis, carbon dioxide, carboxylation, cross-coupling, nickel},\ndoi = {https://doi.org/10.1002/chem.202101082},\nabstract = {Abstract A novel asymmetric nickel-based procedure has been developed in which CO2 fixation is achieved as a second step of a truncated Heck coupling. For this, a new chiral ligand has been prepared and shown to achieve enantiomeric excesses up to 99 \\%. The overall process efficiently furnishes chiral 2,3-dihydrobenzofuran-3-ylacetic acids, an important class of bioactive products, from easy to prepare starting materials. A combined experimental and computational effort revealed the key steps of the catalytic cycle and suggested the unexpected participation of Ni(I) species in the coupling event.},\nyear = {2021}\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2020\n \n \n (8)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Au(III) catalyzes the cross-coupling between activated methylenes and alkene derivatives.\n \n \n \n\n\n \n Castiñeira Reis, M.; Marín-Luna, M.; Janković, N.; Nieto Faza, O.; and Silva López, C.\n\n\n \n\n\n\n Journal of Catalysis, 392: 159-164. 2020.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 2 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{CastineiraReis2020159,\nauthor={Castiñeira Reis, M. and Marín-Luna, M. and Janković, N. and Nieto Faza, O. and Silva López, C.},\ntitle={Au(III) catalyzes the cross-coupling between activated methylenes and alkene derivatives},\njournal={Journal of Catalysis},\nyear={2020},\nvolume={392},\npages={159-164},\ndoi={10.1016/j.jcat.2020.09.030},\nabstract={In the last decade substantial efforts were devoted towards the exploitation of the Au(I) as a promising tool to promote C[sbnd]C bond formation reactions via the activation of unsaturations. Among these efforts, Au(I)/Au(III) cross couplings mediated by a co-oxidant or by photoactivation sit at a privileged position. Au(III) has also shown a rich chemistry but, due to its hardness and lower affinity for unsaturations, it is less often the catalyst of choice in C[sbnd]C bond forming strategies. Surprisingly, we have recently found two examples of cross-coupling reactions in which the authors report to be adding Au(III) to the reaction flask while claiming that Au(I) is the species responsible for the catalytic events. One of such cases even occurs under oxidizing conditions. Here we present a detailed computational study in which we explore the mechanism behind these C[sbnd]C forming reactions. Our results suggest that Au(III) can efficiently catalyze these transformations, thus invoking this exotic reduction is not only unnecessary but also energetically unfavourable.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Experimental and computational study of the 1,5-O → N carbamoyl snieckus-fries-type rearrangement.\n \n \n \n\n\n \n Lopez, C.; Sanz, R.; Feberero, C.; Sedano, C.; and Suarez-Pantiga, S.\n\n\n \n\n\n\n Journal of Organic Chemistry, 85(19): 12561-12578. 2020.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez202012561,\nauthor={Lopez, C.S. and Sanz, R. and Feberero, C. and Sedano, C. and Suarez-Pantiga, S.},\ntitle={Experimental and computational study of the 1,5-O → N carbamoyl snieckus-fries-type rearrangement},\njournal={Journal of Organic Chemistry},\nyear={2020},\nvolume={85},\nnumber={19},\npages={12561-12578},\ndoi={10.1021/acs.joc.0c01732},\nabstract={The reactions of o-lithiated O-aryl N,N-diethylcarbamates with different C-N multiple bond electrophiles have been thoroughly studied. A 1,5-O → N carbamoyl shift, a new variation of the anionic Fries-type rearrangement, takes place when nitriles, imines, or alkylcarbodiimides are employed. In these cases, the carbamoyl group plays a dual role as a directing group, building up a variety of functional groups through the 1,5-O → N carbamoyl migration. On the other hand, the use of iso(thio)cyanates and arylcarbodiimides led to non-rearranged o-functionalized Oarylcarbamates. This reactivity was further computationally explored, and the governing factor could be traced back to the relative basicity of the alternative products (migrated vs nonmigrated substrates). This exploration also provided interesting insights about the degree of complexation of the lithium cations onto these substrates. A new access to useful 2-hydroxybenzophenone derivatives has also been developed. },\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n The effect of solvation in torquoselectivity: Ring opening of monosubstituted cyclobutenes.\n \n \n \n\n\n \n Saadat, K.; Villar López, R.; Shiri, A.; Nieto Faza, O.; and Silva López, C.\n\n\n \n\n\n\n Organic and Biomolecular Chemistry, 18(32): 6287-6296. 2020.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Saadat20206287,\nauthor={Saadat, K. and Villar López, R. and Shiri, A. and Nieto Faza, O. and Silva López, C.},\ntitle={The effect of solvation in torquoselectivity: Ring opening of monosubstituted cyclobutenes},\njournal={Organic and Biomolecular Chemistry},\nyear={2020},\nvolume={18},\nnumber={32},\npages={6287-6296},\ndoi={10.1039/d0ob01229g},\nabstract={The paradigmatic electrocyclic ring opening of monosubstituted cyclobutenes has been used to diagnose possible solvation effects tuning the torquoselectivity observed in these reactions. This kind of selectivity in electrocyclic reactions is mostly due to strong orbital interactions, particularly when they involve powerful electron donors and acceptors, which also combine with usually milder steric effects. Orbital interactions are established between the cleaving C-C bond and the HOMO/LUMO of the EDG/EWG substituent. This implies that the larger torquoselectivity-featuring substrates may also suffer stronger solvation effects due to the higher polarity imposed by the substituent. This premise is tested and the source of solvation effects as a consequence of substitution analyzed. },\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Site-selective synthesis of 1,3-dioxin-3-ones: Via a gold(I) catalyzed cascade reaction.\n \n \n \n\n\n \n An, J.; Pedrazzani, R.; Monari, M.; Marin-Luna, M.; Lopez, C.; and Bandini, M.\n\n\n \n\n\n\n Chemical Communications, 56(56): 7734-7737. 2020.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{An20207734,\nauthor={An, J. and Pedrazzani, R. and Monari, M. and Marin-Luna, M. and Lopez, C.S. and Bandini, M.},\ntitle={Site-selective synthesis of 1,3-dioxin-3-ones: Via a gold(I) catalyzed cascade reaction},\njournal={Chemical Communications},\nyear={2020},\nvolume={56},\nnumber={56},\npages={7734-7737},\ndoi={10.1039/d0cc02703k},\nabstract={A novel gold(i)-catalyzed protocol for the synthesis of 4H-1,3-dioxin-3-ones is presented. The protocol exploits a metal induced cascade sequence involving a [3,3]-sigmatropic rearrangement followed by regioselective O-annulation reactions. A wide range of oxygen-based heterocyclic scaffolds (21 examples) were achieved in excellent yield (up to 80\\%) and a detailed computational investigation as well as deuterium-labelling investigations enabled all the plausible reaction pathways to be mapped and the rationalization of the recorded regioselectivity. },\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Unlocking the 5-exo Pathway with the Au(I)-Catalyzed Alkoxycyclization of 1,3-Dien-5-ynes.\n \n \n \n\n\n \n Virumbrales, C.; Suárez-Pantiga, S.; Marín-Luna, M.; Silva López, C.; and Sanz, R.\n\n\n \n\n\n\n Chemistry - A European Journal, 26(38): 8443-8451. 2020.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Virumbrales20208443,\nauthor={Virumbrales, C. and Suárez-Pantiga, S. and Marín-Luna, M. and Silva López, C. and Sanz, R.},\ntitle={Unlocking the 5-exo Pathway with the Au(I)-Catalyzed Alkoxycyclization of 1,3-Dien-5-ynes},\njournal={Chemistry - A European Journal},\nyear={2020},\nvolume={26},\nnumber={38},\npages={8443-8451},\ndoi={10.1002/chem.202001296},\nabstract={The first general regio- and stereoselective 5-exo gold(I)-catalyzed alkoxycyclization of a specific class of 1,5-enynes such as 1,3-dien-5-ynes has been described, despite 1,5-enynes being known to almost invariably proceed via endo cyclizations under gold-catalysis. The configuration of the terminal alkene in the starting 1,3-dien-5-yne plays a crucial role on the regiochemical outcome of the reaction. A wide variety of interesting alkoxy-functionalized alkylidenecyclopentenes have been synthesized from 1-monosubstituted (E)-1,3-dien-5-ynes. On the contrary, the corresponding Z isomers evolve affording formal 6-endo cyclization products. In addition, mechanistic exploration supports a highly stabilized carbocation as a key intermediate instead of a highly constrained cyclopropyl gold carbene from E isomers, and also accounts for the well differentiated reactivity observed between both E/Z geometrical isomers as well as for the stereochemical outcome of the reaction.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Photochemically Driven Tandem Process in the Construction of a Biscyclopropylcage from 2,5-Dimethoxy- p-benzoquinone and Terminal Acetylenes.\n \n \n \n\n\n \n Álvarez-García, J.; Rubio-Pisabarro, V.; Silva López, C.; and Cid, M.\n\n\n \n\n\n\n Organic Letters, 22(11): 4527-4531. 2020.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Alvarez-Garcia20204527,\nauthor={Álvarez-García, J. and Rubio-Pisabarro, V. and Silva López, C. and Cid, M.M.},\ntitle={Photochemically Driven Tandem Process in the Construction of a Biscyclopropylcage from 2,5-Dimethoxy- p-benzoquinone and Terminal Acetylenes},\njournal={Organic Letters},\nyear={2020},\nvolume={22},\nnumber={11},\npages={4527-4531},\ndoi={10.1021/acs.orglett.0c01554},\nabstract={A photochemical two-step one-pot synthesis of novel biscyclopropyl-box-shaped compounds via the reaction of 2,5-dimethoxy-para-benzoquinone and monosubstituted alkynes is reported. The reaction mechanism for a process in which six new C-C bonds are formed is explored by means of experimental and computational techniques. The whole process occurs with complete selectivity, and only one densely decorated diastereomer is obtained; such a degree of control and substitution makes for a rather powerful and complexity-building process. },\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n The key role of protodeauration in the gold-catalyzed reaction of 1,3-diynes with pyrrole and indole to form complex heterocycles.\n \n \n \n\n\n \n Stylianakis, I.; Nieto Faza, O.; López, C.; and Kolocouris, A.\n\n\n \n\n\n\n Organic Chemistry Frontiers, 7(8): 997-1005. 2020.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Stylianakis2020997,\nauthor={Stylianakis, I. and Nieto Faza, O. and López, C.S. and Kolocouris, A.},\ntitle={The key role of protodeauration in the gold-catalyzed reaction of 1,3-diynes with pyrrole and indole to form complex heterocycles},\njournal={Organic Chemistry Frontiers},\nyear={2020},\nvolume={7},\nnumber={8},\npages={997-1005},\ndoi={10.1039/c9qo01544b},\nabstract={Indole is a very common structural motif in alkaloids, and a number of them feature remarkable bioactive properties. Due to its relevant role in medicinal chemistry and the pharma-industry, many methods for indole synthesis have been developed, but only a few of them exploit the [4 + 2] approach. Recently a successful attempt at indole and carbazole formation via a formal gold mediated [4 + 2] addition of a diyne to pyrrole and indole rings has been reported by Ohno. A number of intriguing features observed in this reaction are however left to be resolved. We study here the mechanism of the Au-catalyzed reaction of 1,3-diynes with pyrrole and indole rings leading to substituted indoles and carbazoles, respectively. The reaction pathways are found to be significantly more complex than we had anticipated, for instance, in the case of the formation of carbazoles, one competitive route involves the formation of an unexpected spirane intermediate that evolves via a 1,2-alkenyl migration. Beyond this complexity, the current study also serves to highlight the importance of fundamental steps that are often disregarded as kinetically irrelevant, such as the protodeauration of reaction intermediates. },\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Acetate-catalyzed hydroboration of CO2 for the selective formation of methanol-equivalent products.\n \n \n \n\n\n \n Sokolovicz, Y.; Nieto Faza, O.; Specklin, D.; Jacques, B.; López, C.; Dos Santos, J.; Schrekker, H.; and Dagorne, S.\n\n\n \n\n\n\n Catalysis Science and Technology, 10(8): 2407-2414. 2020.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Sokolovicz20202407,\nauthor={Sokolovicz, Y.C.A. and Nieto Faza, O. and Specklin, D. and Jacques, B. and López, C.S. and Dos Santos, J.H.Z. and Schrekker, H.S. and Dagorne, S.},\ntitle={Acetate-catalyzed hydroboration of CO2 for the selective formation of methanol-equivalent products},\njournal={Catalysis Science and Technology},\nyear={2020},\nvolume={10},\nnumber={8},\npages={2407-2414},\ndoi={10.1039/d0cy00118j},\nabstract={The present study details the use of the acetate anion, an inexpensive and robust anion, as a CO2 hydroboration catalyst for the selective formation, in most cases, of methanol-equivalent borane products. Thus, upon heating (90 °C, PhBr), tetrabutylammonium, sodium and potassium acetate (1, 2 and 3, respectively) effectively catalyze CO2 hydroboration by pinacolborane (pinB-H) to afford CO2 reduction products HOCOBpin (A), pinBOCH2OBpin (B) and methoxyborane (C). In most cases, high selectivity for product C with higher borane loading and longer reaction time with a TON of up to 970 was observed. The reduction catalysis remains efficient at low catalyst loading (down to 0.1 mol%) and may also be performed under solvent-free conditions using salt 1 as a catalyst, reflecting the excellent robustness and stability of the acetate anion. In control experiments, a 1/1 1/pinB-H mixture was found to react fast with CO2 at room temperature to produce formate species [pinB(O2CH)(OAc)][N(nBu)4] (5) through CO2 insertion into the B-H bond. DFT calculations were also performed to gain insight into the acetate-mediated CO2 hydroboration catalysis, which further supported the crucial role of acetate as a Lewis base in CO2 functionalization catalysis by pinB-H. The DFT-estimated mechanism is in line with experimental data and rationalizes the formation of the most thermodynamically stable reduction product C through acetate catalysis. },\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2019\n \n \n (9)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n On the use of popular basis sets: Impact of the intramolecular basis set superposition error.\n \n \n \n\n\n \n Vidal, Á.; De Vicente Poutás, L.; Faza, O.; and López, C.\n\n\n \n\n\n\n Molecules, 24(20): 3810. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Vidal2019,\nauthor={Vidal, Á.V. and De Vicente Poutás, L.C. and Faza, O.N. and López, C.S.},\ntitle={On the use of popular basis sets: Impact of the intramolecular basis set superposition error},\njournal={Molecules},\nyear={2019},\nvolume={24},\nnumber={20},\ndoi={10.3390/molecules24203810},\npages={3810},\nabstract={The magnitude of intramolecular basis set superposition error (BSSE) is revealed via computing systematic trends in molecular properties. This type of error is largely neglected in the study of the chemical properties of small molecules and it has historically been analyzed just in the study of large molecules and processes dominated by non-covalent interactions (typically dimerization or molecular complexation and recognition events). In this work we try to provide proof of the broader prevalence of this error, which permeates all types of electronic structure calculations, particularly when employing insufficiently large basis sets. },\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Gold(I)-catalyzed nucleophilic cyclization of β-monosubstituted: O -(alkynyl)styrenes: A combined experimental and computational study.\n \n \n \n\n\n \n Virumbrales, C.; Solas, M.; Suárez-Pantiga, S.; Fernández-Rodríguez, M.; Marín-Luna, M.; López, C.; and Sanz, R.\n\n\n \n\n\n\n Organic and Biomolecular Chemistry, 17(46): 9924-9932. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Virumbrales20199924,\nauthor={Virumbrales, C. and Solas, M. and Suárez-Pantiga, S. and Fernández-Rodríguez, M.A. and Marín-Luna, M. and López, C.S. and Sanz, R.},\ntitle={Gold(I)-catalyzed nucleophilic cyclization of β-monosubstituted: O -(alkynyl)styrenes: A combined experimental and computational study},\njournal={Organic and Biomolecular Chemistry},\nyear={2019},\nvolume={17},\nnumber={46},\npages={9924-9932},\ndoi={10.1039/c9ob02126d},\nabstract={The stereospecific gold(i)-catalyzed nucleophilic cyclization of β-monosubstituted o-(alkynyl)styrenes to produce C-1 functionalized 1H-indenes including challenging substrates and nucleophiles, such as β-(cyclo)alkyl-substituted o-(alkynyl)styrenes and a variety of alcohols as well as selected electron-rich aromatics, is reported. DFT calculations support the stereochemical outcome of the process that involves the formation of a key cyclopropyl gold carbene intermediate through a regiospecific 5-endo cyclization. },\n}\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Double Protonation of a cis-Bipyridoallenophane Detected via Chiral-Sensing Switch: The Role of Ion Pairs.\n \n \n \n\n\n \n Castro-Fernández, S.; Álvarez-García, J.; García-Río, L.; Silva-López, C.; and Cid, M. M.\n\n\n \n\n\n\n Organic Letters, 21(15): 5898-5902. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{doi:10.1021/acs.orglett.9b02024,\nauthor = {Castro-Fernández, Silvia and Álvarez-García, Jonathan and García-Río, Luís and Silva-López, Carlos and Cid, María Magdalena},\ntitle = {Double Protonation of a cis-Bipyridoallenophane Detected via Chiral-Sensing Switch: The Role of Ion Pairs},\njournal = {Organic Letters},\nvolume = {21},\nnumber = {15},\npages = {5898-5902},\nyear = {2019},\ndoi = {10.1021/acs.orglett.9b02024},\nabstract = { We prove that the confinement of the conformational space of pyridoallenophanes leads to intense chiroptical responses. Unlike the cyclic dimer [142], single-conformation [141]pyridoallenophanes isomerize under thermal and photochemical conditions. Yet, less-strained [141]-bipyridoallenophanes are stable and are prepared successfully. They, unexpectedly, undergo double protonation as a result of cooperative ion-pairing and hydrogen bonding. The complex formation forces a single configuration of the axis connecting both pyridyl rings recognized by a diagnostic circular dichroism (CD) signal at 330 nm. }\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Computational and experimental studies on Cu/Au-catalyzed stereoselective synthesis of 1,3-disubstituted allenes.\n \n \n \n\n\n \n Cid, M.; Lago-Silva, M.; Comesaña, M.; Nieto Faza, O.; and López, C.\n\n\n \n\n\n\n Organic Chemistry Frontiers, 6(11): 1780-1786. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Cid20191780,\nauthor={Cid, M.M. and Lago-Silva, M. and Comesaña, M.G. and Nieto Faza, O. and López, C.S.},\ntitle={Computational and experimental studies on Cu/Au-catalyzed stereoselective synthesis of 1,3-disubstituted allenes},\njournal={Organic Chemistry Frontiers},\nyear={2019},\nvolume={6},\nnumber={11},\npages={1780-1786},\ndoi={10.1039/c9qo00364a},\nabstract={Cu- and Au-mediated formation of allenes from terminal alkynes and aldehydes via propargylamine intermediates is hampered by reversibility in the propargylamine formation. The use of a stable Au(i) catalyst in the reaction using a chiral propargylamine provided clues to disentangle the mechanism of the whole process that would have been otherwise hidden. Additionally, the process was observed to be stereoselective when an enantiomerically pure chiral propargylamine was used as starting substrate providing the corresponding 1,3-disubstituted allenes with high enantiomeric ratio. © 2019 the Partner Organisations.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Lennard-Jones Intermolecular Potentials for the Description of 6-Membered Aromatic Heterocycles Interacting with the Isoelectronic CO2 and CS2.\n \n \n \n\n\n \n Vidal-Vidal, Á.; Silva López, C.; and Faza, O.\n\n\n \n\n\n\n Journal of Physical Chemistry A, 123(20): 4475-4485. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Vidal-Vidal20194475,\nauthor={Vidal-Vidal, Á. and Silva López, C. and Faza, O.N.},\ntitle={Lennard-Jones Intermolecular Potentials for the Description of 6-Membered Aromatic Heterocycles Interacting with the Isoelectronic CO2 and CS2},\njournal={Journal of Physical Chemistry A},\nyear={2019},\nvolume={123},\nnumber={20},\npages={4475-4485},\ndoi={10.1021/acs.jpca.9b00375},\nabstract={We have generated Lennard-Jones potentials for the interaction between CX2 (X = O, S) and 11 nitrogen-doped benzene derivatives in different orientations at the M06-2X/def2-tzvpp level as tools to parametrize accurate force fields and to better understand the interaction of these greenhouse gases with heterocyclic building blocks used in the design of capture and detection systems. We find that the most favorable interactions are found between the carbon in CO2 and the main heterocycle in the ring in a parallel orientation, whereas the preferred interaction mode of CS2 is established between sulfur and the πdensity of the aromatic ring. The fact that the preferences for interaction sites and orientations of CO2 and CS2 are most of the times opposite helps in terms of ensuring the selectivity of these systems in front of these two isoelectronic compounds. The existence of very good linear correlations (R2 values very close to one) between the number of nitrogen atoms in the heterocyclic ring and the depth of the interaction potential wells opens the door to the use of these results in generating coarse-grained potentials or models with predictive power for use in the design of larger systems. © Copyright © 2019 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Phosphine-Catalyzed Stereoselective Dearomatization of 3-NO2 -Indoles with Allenoates.\n \n \n \n\n\n \n Cerveri, A.; Faza, O.; López, C.; Grilli, S.; Monari, M.; and Bandini, M.\n\n\n \n\n\n\n Journal of Organic Chemistry, 84(10): 6347-6355. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Cerveri20196347,\nauthor={Cerveri, A. and Faza, O.N. and López, C.S. and Grilli, S. and Monari, M. and Bandini, M.},\ntitle={Phosphine-Catalyzed Stereoselective Dearomatization of 3-NO2 -Indoles with Allenoates},\njournal={Journal of Organic Chemistry},\nyear={2019},\nvolume={84},\nnumber={10},\npages={6347-6355},\ndoi={10.1021/acs.joc.9b00559},\nabstract={The stereoselective phosphine-catalyzed ((pMeOC 6 H 4 ) 3 P, 10-20 mol \\%) dearomatization of 3-NO 2 -indoles with allenoates is described. A range of densely functionalized indolines (18 examples) is obtained in high yields (up to 96\\%) under mild reaction conditions (rt, air, reagent-grade solvent). Computational simulations and labeling experiments revealed a stepwise [3 + 2]-type mechanism involving a water-assisted hydrogen shift and accounted for the diastereoselection recorded. © 2019 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Methanol directing the dual reactivity of 1,3-dien-5-ynes under gold(I) catalysis: A computational study.\n \n \n \n\n\n \n Marín-Luna, M.; Bolaño, I.; Silva López, C.; and Nieto Faza, O.\n\n\n \n\n\n\n Computational and Theoretical Chemistry, 1148: 33-37. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Marin-Luna201933,\nauthor={Marín-Luna, M. and Bolaño, I. and Silva López, C. and Nieto Faza, O.},\ntitle={Methanol directing the dual reactivity of 1,3-dien-5-ynes under gold(I) catalysis: A computational study},\njournal={Computational and Theoretical Chemistry},\nyear={2019},\nvolume={1148},\npages={33-37},\ndoi={10.1016/j.comptc.2018.11.010},\nabstract={The presence of methanol on gold(I)-mediated cycloisomerizations of substituted 1,3-dien-5-ynes provokes the formation of 5-alkoxycyclopentadiene rather than a substituted benzene, which is the isolated product in absence of the alcohol substrate. Calculations indicate that both mechanistic routes start with a 5-endo-dig cyclization of the initial activated-dienyne leading to a bicyclic substrate. This common intermediate then experiments either a tandem ring-expansion/Wagner–Meerwein rearragement process leading to the final benzene or it is attacked by the MeOH molecule leading to the alkoxycyclopentadiene. The kinetic preference along with the high concentration of MeOH used in the reaction would be responsible for the different pathways found in this kind of enynes. © 2018},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Pushing the limits of concertedness. A waltz of wandering carbocations.\n \n \n \n\n\n \n Castiñeira Reis, M.; López, C.; Nieto Faza, O.; and Tantillo, D.\n\n\n \n\n\n\n Chemical Science, 10(7): 2159-2170. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{CastineiraReis20192159,\nauthor={Castiñeira Reis, M. and López, C.S. and Nieto Faza, O. and Tantillo, D.J.},\ntitle={Pushing the limits of concertedness. A waltz of wandering carbocations},\njournal={Chemical Science},\nyear={2019},\nvolume={10},\nnumber={7},\npages={2159-2170},\ndoi={10.1039/c8sc03567a},\nabstract={Among the array of complex terpene-forming carbocation cyclization/rearrangement reactions, the so-called “triple shift” reactions are among the most unexpected. Such reactions involve the asynchronous combination of three 1,n-shifts into a concerted process, e.g., a 1,2-alkyl shift followed by a 1,3-hydride shift followed by a second 1,2-alkyl shift. This type of reaction so far has been proposed to occur during the biosynthesis of diterpenes and the sidechains of sterols. Here we describe efforts to push the limits of concertedness in this type of carbocation reaction by designing, and characterizing with quantum chemical computations, systems that could couple additional 1,n-shift events to a triple shift leading, in principle to quadruple, pentuple, etc. shifts. While our designs did not lead to clear-cut examples of quadruple, etc. shifts, they did lead to reactions with surprisingly flat energy surfaces where more than five chemical events connect reactants and plausible products. Ab initio molecular dynamics simulations demonstrate that the formal minima on these surfaces interchange on short timescales, both with each other and with additional unexpected structures, allowing us a glimpse into a very complex manifold that allows ready access to great structural diversity. © The Royal Society of Chemistry.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Scandium catalysed stereoselective thio-allylation of allenyl-imidates.\n \n \n \n\n\n \n Parodi, A.; Battaglioli, S.; Liu, Y.; Monari, M.; Marín-Luna, M.; Silva-López, C.; and Bandini, M.\n\n\n \n\n\n\n Chemical Communications, 55(65): 9669-9672. 2019.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Parodi20199669,\nauthor={Parodi, A. and Battaglioli, S. and Liu, Y. and Monari, M. and Marín-Luna, M. and Silva-López, C. and Bandini, M.},\ntitle={Scandium catalysed stereoselective thio-allylation of allenyl-imidates},\njournal={Chemical Communications},\nyear={2019},\nvolume={55},\nnumber={65},\npages={9669-9672},\ndoi={10.1039/c9cc04302k},\nabstract={The site-selective thio-allylation of electron-deficient 1,2-dienes is documented under scandium catalysis. The methodology enables the realization of α-β unsaturated, β-thio, γ-allyl carboxylic acid derivatives via a one-pot Lewis acid promoted Michael addition/[3,3]-sigmatropic rearrangement sequence (20 examples) in high yields (up to 95\\%). Full rationalization of the reaction mechanism and stereochemical outcome is provided via DFT simulations. © The Royal Society of Chemistry 2019.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2018\n \n \n (5)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Rational Design of Efficient Environmental Sensors: Ring-Shaped Nanostructures Can Capture Quat Herbicides.\n \n \n \n\n\n \n Vidal-Vidal, Á.; Cabaleiro-Lago, E.; Silva López, C.; and Faza, O.\n\n\n \n\n\n\n ACS Omega, 3(12): 16976-16988. 2018.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Vidal-Vidal201816976,\nauthor={Vidal-Vidal, Á. and Cabaleiro-Lago, E.M. and Silva López, C. and Faza, O.N.},\ntitle={Rational Design of Efficient Environmental Sensors: Ring-Shaped Nanostructures Can Capture Quat Herbicides},\njournal={ACS Omega},\nyear={2018},\nvolume={3},\nnumber={12},\npages={16976-16988},\ndoi={10.1021/acsomega.8b02673},\nabstract={The viability of using [n]-cycloparaphenylenes (CPPs) of different sizes to encapsulate diquat (DQ) pesticide molecules has been tested analyzing the origin of the host-guest interactions stabilizing the complex. This analysis provides rational design capabilities to construct ad hoc capturing systems tailored to the desired pollutant. All CPPs considered (n = 7-12) are capable of forming remarkably stable complexes with DQ, though [9]-CPP is the best candidate, where a fine balance is established between the energy penalty due to the deformation + repulsion of the pesticide molecule inside the cavity (larger in smaller CPPs) and the maximization of the favorable dispersion, electrostatic and induction contributions (which also decrease in larger rings). These encouraging results prompted us to evaluate the potential of using Resonance Raman spectroscopy on nanohoop complexes as a tool for DQ sensing. The shifts observed in the vibrational frequencies of DQ upon complexation allow us to determine whether complexation has been achieved. Additionally, a large enhancement of the signals permits a selective identification of the vibrational modes. © 2018 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Nickel catalyzed regio- and stereoselective arylation and methylation of allenamides via coupling reactions. An experimental and computational study.\n \n \n \n\n\n \n Liu, Y.; Cerveri, A.; De Nisi, A.; Monari, M.; Nieto Faza, O.; Lopez, C.; and Bandini, M.\n\n\n \n\n\n\n Organic Chemistry Frontiers, 5(22): 3231-3239. 2018.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Liu20183231,\nauthor={Liu, Y. and Cerveri, A. and De Nisi, A. and Monari, M. and Nieto Faza, O. and Lopez, C.S. and Bandini, M.},\ntitle={Nickel catalyzed regio- and stereoselective arylation and methylation of allenamides via coupling reactions. An experimental and computational study},\njournal={Organic Chemistry Frontiers},\nyear={2018},\nvolume={5},\nnumber={22},\npages={3231-3239},\ndoi={10.1039/c8qo00729b},\nabstract={The nickel catalyzed regio- and stereoselective condensation of boronic acids to allenamides is documented as a novel synthetic route to stereochemically defined tri-substituted enamides. The protocol has been implemented into a three-component variant intercepting the in situ formed allyl-Ni intermediate with a range of aldehydes. Additionally, evidence for the effective extension of this methodology to Me2Zn is documented. Full rationale on the mechanism as well as its stereochemical outcome is provided by a synergistic experimental/computational approach. © the Partner Organisations.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Mechanism of the Molybdenum-Mediated Cadogan Reaction.\n \n \n \n\n\n \n Castiñeira Reis, M.; Marín-Luna, M.; Silva López, C.; and Faza, O.\n\n\n \n\n\n\n ACS Omega, 3(6): 7019-7026. 2018.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{CastineiraReis20187019,\nauthor={Castiñeira Reis, M. and Marín-Luna, M. and Silva López, C. and Faza, O.N.},\ntitle={Mechanism of the Molybdenum-Mediated Cadogan Reaction},\njournal={ACS Omega},\nyear={2018},\nvolume={3},\nnumber={6},\npages={7019-7026},\ndoi={10.1021/acsomega.8b01278},\nabstract={Oxygen atom transfer reactions are receiving increasing attention because they bring about paramount transformations in the current biomass processing industry. Significant efforts have therefore been made lately in the development of efficient and scalable methods to deoxygenate organic compounds. One recent alternative involves the modification of the Cadogan reaction in which a Mo(VI) core catalyzes the reduction of o-nitrostyrene derivatives to indoles in the presence of PPh3. We have used density functional theory calculations to perform a comprehensive mechanistic study on this transformation, in which we find two clearly defined stages: an associative path from the nitro to the nitroso compound, characterized by the reduction of the catalyst in the first step, and a peculiar mechanism involving oxazaphosphiridine and nitrene intermediates leading to an indole product, where the metal catalyst does not participate. © Copyright 2018 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Solvation.\n \n \n \n\n\n \n López, C.; and Faza, O.\n\n\n \n\n\n\n 2018.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@BOOK{Lopez201897,\nauthor={López, C.S. and Faza, O.N.},\ntitle={Solvation},\njournal={Applied Theoretical Organic Chemistry},\nyear={2018},\npages={97-146},\ndoi={10.1142/9781786344090_0004},\n}\n\n

\n

\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Nitrogen doped nanohoops as promising CO2 capturing devices.\n \n \n \n\n\n \n Vidal Vidal, Á.; López, C.; and Nieto Faza, O.\n\n\n \n\n\n\n Physical Chemistry Chemical Physics, 20(13): 8607-8615. 2018.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{VidalVidal20188607,\nauthor={Vidal Vidal, Á. and López, C.S. and Nieto Faza, O.},\ntitle={Nitrogen doped nanohoops as promising CO2 capturing devices},\njournal={Physical Chemistry Chemical Physics},\nyear={2018},\nvolume={20},\nnumber={13},\npages={8607-8615},\ndoi={10.1039/c7cp08498f},\nabstract={The impact of climate change in the face of steady or increasing emissions has made the capture and storage of CO2 a priority issue. Supramolecular chemistry is one of the tools that can be used for this task, due to the possibility of tuning intermolecular interactions for the capture of this gas in a selective and efficient way. In this context, this work presents a novel approach for the capture of CO2 based on n-cycloparaphenylenes ([n]-CPPs) doped with nitrogen atoms. This is the first time that the potential of these structures for the capture of polluting gases has been evaluated. Among all the structures analysed, the one yielding the best results (complexation energy of -32.80 kJ mol-1) contains 4 nitrogen atoms per monomer. The topology of the electron density of the host-guest complex and the nature of its non-covalent interactions have been analyzed in this work in order to explain this high binding energy and identify potential structural modifications to improve it. The capability of this system to be used as a sensing device for CO2 using vibrational spectroscopy is also explored. © 2018 the Owner Societies.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2017\n \n \n (9)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Lennard-Jones Potentials for the Interaction of CO$_2$ with Five-Membered Aromatic Heterocycles.\n \n \n \n\n\n \n Vidal-Vidal, Á.; Silva López, C.; and Faza, O.\n\n\n \n\n\n\n Journal of Physical Chemistry A, 121(49): 9518-9530. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Vidal-Vidal20179518,\nauthor={Vidal-Vidal, Á. and Silva López, C. and Faza, O.N.},\ntitle={Lennard-Jones Potentials for the Interaction of CO$_2$ with Five-Membered Aromatic Heterocycles},\njournal={Journal of Physical Chemistry A},\nyear={2017},\nvolume={121},\nnumber={49},\npages={9518-9530},\ndoi={10.1021/acs.jpca.7b09382},\nabstract={We used M06-2X/Def2-TZVPP to calculate a broad set of rigid interaction profiles between CO2 and 30 different aromatic heterocycles, based on pyrrole, furan, and thiophene with ring positions subsituted with up to four nitrogens. For each system, several orientations of the fragments were explored to both find the preferred interaction mode and have information about other interaction modes that can contribute to the binding energy when CO2 is captured by complex systems. From these data, Lennard-Jones potentials were obtained, which can be used for the parametrization of force fields that correctly describe the multipolar and dispersion interactions at play between these kinds of fragments. These results are expected to contribute to the development of new force fields for the study of chemical systems for the capture and sequestration of CO2 and also directly for the design of such systems.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Gold-Catalyzed Dearomatization of 2-Naphthols with Alkynes.\n \n \n \n\n\n \n An, J.; Parodi, A.; Monari, M.; Reis, M.; Lopez, C.; and Bandini, M.\n\n\n \n\n\n\n Chemistry - A European Journal, 23(69): 17473-17477. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{An201717473,\nauthor={An, J. and Parodi, A. and Monari, M. and Reis, M.C. and Lopez, C.S. and Bandini, M.},\ntitle={Gold-Catalyzed Dearomatization of 2-Naphthols with Alkynes},\njournal={Chemistry - A European Journal},\nyear={2017},\nvolume={23},\nnumber={69},\npages={17473-17477},\ndoi={10.1002/chem.201704942},\nabstract={The site-selective dearomatization of naphthols is realized in a straightforward manner through a gold(I)-catalyzed [3,3]-sigmatropic rearrangement/allene functionalization cascade sequence. The method employs readily available naphthylpropargyl ethers as starting materials. A range of densely functionalized dihydrofurylnaphthalen-2(1H)-ones are obtained in high yields (up to 98 \\%) and extremely mild reaction conditions (reagent grade solvent, air, 10 minute reaction time). A complete theoretical elucidation of the reaction machinery is also proposed, providing a rationale for important issues such as regio- and chemoselectivity.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n CO$_2$ Complexes with Five-Membered Heterocycles: Structure, Topology, and Spectroscopic Characterization.\n \n \n \n\n\n \n Vidal-Vidal, Á.; Faza, O.; and Silva López, C.\n\n\n \n\n\n\n Journal of Physical Chemistry A, 121(47): 9118-9130. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Vidal-Vidal20179118,\nauthor={Vidal-Vidal, Á. and Faza, O.N. and Silva López, C.},\ntitle={CO$_2$ Complexes with Five-Membered Heterocycles: Structure, Topology, and Spectroscopic Characterization},\njournal={Journal of Physical Chemistry A},\nyear={2017},\nvolume={121},\nnumber={47},\npages={9118-9130},\ndoi={10.1021/acs.jpca.7b09394},\nabstract={In a first step toward the rational design of macrocyclic structures optimized for CO2 capture, we systematically explored the potential of 30 five-membered aromatic heterocycles to establish coordinating complexes with this pollutant. The interactions between the two moieties were studied in several orientations, and the obtained complexes were analyzed in terms of electron density and vibrational fingerprint. The former is an aid to provide an in-depth knowledge of the interaction, whereas the latter should help to select structural motifs that have not only good complexation properties but also diagnostic spectroscopic signals.},\n}\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n [MoO$_2$]$^{2+}$-Mediated Oxygen Atom Transfer via an Unusual Lewis Acid Mechanism.\n \n \n \n\n\n \n Castiñeira Reis, M.; Marín-Luna, M.; Silva López, C.; and Faza, O.\n\n\n \n\n\n\n Inorganic Chemistry, 56(17): 10570-10575. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{CastineiraReis201710570,\nauthor={Castiñeira Reis, M. and Marín-Luna, M. and Silva López, C. and Faza, O.N.},\ntitle={[MoO$_2$]$^{2+}$-Mediated Oxygen Atom Transfer via an Unusual Lewis Acid Mechanism},\njournal={Inorganic Chemistry},\nyear={2017},\nvolume={56},\nnumber={17},\npages={10570-10575},\ndoi={10.1021/acs.inorgchem.7b01529},\nabstract={Density functional theory is applied to the study of the oxygen atom transfer reaction from sulfoxide (DMSO) to phosphine (PMe3) catalyzed by the [MoO2]2+ active core. In this work, two fundamentally different roles are explored for this dioxometal complex in the first step of the catalytic cycle: as an oxidizing agent and as a Lewis acid. The latter turns out to be the favored pathway for the oxygen atom transfer. This finding may have more general implications for similar reactions catalyzed by the same [MoO2]2+ core. © 2017 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n From Hydrindane to Decalin: A Mild Transformation through a Dyotropic Ring Expansion.\n \n \n \n\n\n \n Santalla, H.; Faza, O.; Gómez, G.; Fall, Y.; and Silva López, C.\n\n\n \n\n\n\n Organic Letters, 19(13): 3648-3651. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Santalla20173648,\nauthor={Santalla, H. and Faza, O.N. and Gómez, G. and Fall, Y. and Silva López, C.},\ntitle={From Hydrindane to Decalin: A Mild Transformation through a Dyotropic Ring Expansion},\njournal={Organic Letters},\nyear={2017},\nvolume={19},\nnumber={13},\npages={3648-3651},\ndoi={10.1021/acs.orglett.7b01621},\nabstract={An unexpected ring expansion converting hydrindane cores into decalins has been observed. The process occurs under very mild conditions and with exquisite transfer of chiral information. The ring expansion provides access to decorated decalins with complete stereocontrol. The reaction mechanism is studied in order to gain insight into the underlying causes for the low thermal requirements in this reaction and the nature of the chirality transfer process. Interestingly, both result from an unprecedented dyotropic reaction involving a mesylate group. © 2017 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Dynamic Effects Responsible for High Selectivity in a [3,3] Sigmatropic Rearrangement Featuring a Bispericyclic Transition State.\n \n \n \n\n\n \n Villar López, R.; Faza, O.; and Silva López, C.\n\n\n \n\n\n\n Journal of Organic Chemistry, 82(9): 4758-4765. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{VillarLopez20174758,\nauthor={Villar López, R. and Faza, O.N. and Silva López, C.},\ntitle={Dynamic Effects Responsible for High Selectivity in a [3,3] Sigmatropic Rearrangement Featuring a Bispericyclic Transition State},\njournal={Journal of Organic Chemistry},\nyear={2017},\nvolume={82},\nnumber={9},\npages={4758-4765},\ndoi={10.1021/acs.joc.7b00425},\nabstract={Bispericyclic transition states appear when two independent pericyclic transition states merge into one. They are a particular case of the more general ambimodal concept applied to a transition state that connects reactants with two or more products involving reaction path bifurcations through valley-ridge inflections. In the present computational work, the first example of a bifurcating sigmatropic reaction featuring a bispericyclic transition state is reported for a cyclohexane featuring opposing methylene and a vinylidene fragments. Perhalogenation of a C-C bond in this substrate imparts a strong desymmetrization to the bifurcating potential energy surface. These systems undergo the [3,3] sigmatropic rearrangement with high selectivity, with a preferred product that depends on which halogen decorates the C-C bond. We have found that dynamic effects have a paramount role in the selectivity observed for these reactions. © 2017 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Three Reaction Channels with Signature Proton Transfers in the Ni(I)-Catalyzed Decomposition of Ethyl Acetate.\n \n \n \n\n\n \n Silva López, C.; Faza, O.; Mansell, A.; Theis, Z.; and Bellert, D.\n\n\n \n\n\n\n Organometallics, 36(4): 761-766. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{SilvaLopez2017761,\nauthor={Silva López, C. and Faza, O.N. and Mansell, A. and Theis, Z. and Bellert, D.},\ntitle={Three Reaction Channels with Signature Proton Transfers in the Ni(I)-Catalyzed Decomposition of Ethyl Acetate},\njournal={Organometallics},\nyear={2017},\nvolume={36},\nnumber={4},\npages={761-766},\ndoi={10.1021/acs.organomet.6b00769},\nabstract={The decomposition of ethyl acetate catalyzed by Ni(I) has been investigated in the gas phase both experimentally and computationally. This approach allows us to determine what is the bare effect of the metal center in the catalytic process, without the intervention of environmental factors such as solvent, ligands, counterions, etc. This reaction is found to exhibit three competitive channels affording different products: ketene or ethanol, two units of acetaldehyde, and acetic acid or ethylene. Interestingly, each of these channels involves a characteristic hydrogen shift as the key step on the catalytic process: an inner-sphere H shift, an outer-sphere shift, and a peculiar orbital-like motion that merits careful characterization. © 2017 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Cycloreversion of the CO$_2$ trimer: a paradigmatic pseudopericyclic [2 + 2 + 2] cycloaddition reaction.\n \n \n \n\n\n \n Villar López, R.; Nieto Faza, O.; Matito, E.; and López, C.\n\n\n \n\n\n\n Organic and Biomolecular Chemistry, 15(2): 435-441. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{VillarLopez2017435,\nauthor={Villar López, R. and Nieto Faza, O. and Matito, E. and López, C.S.},\ntitle={Cycloreversion of the CO$_2$ trimer: a paradigmatic pseudopericyclic [2 + 2 + 2] cycloaddition reaction},\njournal={Organic and Biomolecular Chemistry},\nyear={2017},\nvolume={15},\nnumber={2},\npages={435-441},\ndoi={10.1039/c6ob02288j},\nabstract={Very recently, the CO2 trimer has been experimentally synthesized, isolated and characterized. This process opens new ways for the withdrawal and storage of this greenhouse gas. The trimer is reported to be stable up to 40 °C, with a lifetime of about 40 min at this temperature. At these or under harsher thermal conditions it reverts to the three monomers. The mechanism of this reaction has been theoretically studied and the electronic character of the associated transition state has been analyzed from a variety of perspectives (energetic, magnetic, electron localization and delocalization functions) which indicate that it has paradigmatic pseudopericyclic character. To allow for a comparative study, the isoelectronic fragmentations of cyclohexane into three units of ethylene and of benzene into three units of acetylene have been included in this work. The study of a similar series of formally forbidden-four-centered [2 + 2] cycloreversions confirmed the pseudopericyclic nature of these reactions when the CO2 dimer or trimer is involved. © The Royal Society of Chemistry.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Governing effects in the mechanism of the gold-catalyzed cycloisomerization of allenic hydroxylamine derivatives.\n \n \n \n\n\n \n Kiriakidi, S.; Nieto Faza, O.; Kolocouris, A.; and López, C.\n\n\n \n\n\n\n Organic and Biomolecular Chemistry, 15(28): 5920-5926. 2017.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Kiriakidi20175920,\nauthor={Kiriakidi, S. and Nieto Faza, O. and Kolocouris, A. and López, C.S.},\ntitle={Governing effects in the mechanism of the gold-catalyzed cycloisomerization of allenic hydroxylamine derivatives},\njournal={Organic and Biomolecular Chemistry},\nyear={2017},\nvolume={15},\nnumber={28},\npages={5920-5926},\ndoi={10.1039/c7ob01275f},\nabstract={The formation of chiral heterocycles via cycloisomerization reactions of allene derivatives has gained relevance due to their associated efficiency and atom-economy. The only drawback that keeps these reactions away from being routine synthetic strategies is the control in the regioselectivity (most often 5-endo vs. 6-endo). In this work, we computationally explore the experimental chemistry reported by Krause using N-hydroxy-α-aminoallenes and hydroxylamine ethers as substrates and provide a rationale for the different reactivity observed. The drastic effects observed experimentally when changing the nature of the gold catalyst have also been studied mechanistically. These results are expected to help in the design of improved regioselective protocols for the formation of medium sized chiral heterocycles from allene substrates. © 2017 The Royal Society of Chemistry.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2016\n \n \n (9)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Assessing the attractive/repulsive force balance in axial cyclohexane C–Hax···Yax contacts: A combined computational analysis in monosubstituted cyclohexanes.\n \n \n \n\n\n \n Silva Lopez, C.; Nieto Faza, O.; De Proft, F.; and Kolocouris, A.\n\n\n \n\n\n\n Journal of Computational Chemistry,2647-2658. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{SilvaLopez20162647,\nauthor={Silva Lopez, C. and Nieto Faza, O. and De Proft, F. and Kolocouris, A.},\ntitle={Assessing the attractive/repulsive force balance in axial cyclohexane C–Hax···Yax contacts: A combined computational analysis in monosubstituted cyclohexanes},\njournal={Journal of Computational Chemistry},\nyear={2016},\npages={2647-2658},\ndoi={10.1002/jcc.24496},\nabstract={The interactions of axial substituents in monosubstituted cyclohexane rings are studied in this work using an array of different computational techniques. Additionally, the anomalous axial preference for some bulky substituents is related to stabilizing dispersion interactions. We find that the C–Hax···Yax contacts for various substituents with distances ranging from 2 to ∼5 Å may include attractive dispersion forces that can affect the conformational equilibrium; these forces co-exist with Pauli repulsive forces effected by Yax group due to van der Waals sphere penetration. At distances between 2 and 3 Å stabilizing electron transfer interactions were calculated and the combination of natural bond orbital and QTAIM analysis showed that, in certain cases, Yax = tBu, Cax–O or Cax = O or Sax = O or Cax = S this interaction can be characterized as an improper H-bond. DFT-D3 and non-covalent interactions calculations (NCIs) in cyclohexane derivatives with Yax = SiOR3 including HYax···Hcy surfaces at distances ranging between 4 and 6 Å suggest that dispersion has a clear effect on the experimentally observed stabilization of the axial conformer. NCIs computed from the reduced density gradient help to visually identify and analyze these interactions. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n A Radical Mechanism for the Vanadium-Catalyzed Deoxydehydration of Glycols.\n \n \n \n\n\n \n De Vicente Poutás, L.; Castiñeira Reis, M.; Sanz, R.; López, C.; and Faza, O.\n\n\n \n\n\n\n Inorganic Chemistry, 55(21): 11372-11382. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{DeVicentePoutas201611372,\nauthor={De Vicente Poutás, L.C. and Castiñeira Reis, M. and Sanz, R. and López, C.S. and Faza, O.N.},\ntitle={A Radical Mechanism for the Vanadium-Catalyzed Deoxydehydration of Glycols},\njournal={Inorganic Chemistry},\nyear={2016},\nvolume={55},\nnumber={21},\npages={11372-11382},\ndoi={10.1021/acs.inorgchem.6b01916},\nabstract={We propose a novel mechanism for the deoxydehydration (DODH) reaction of glycols catalyzed by a [Bu4N][VO2(dipic)] complex (dipic = pyridine-2,6-dicarboxylate) using triphenylphosphine as a reducing agent. Using density functional theory, we have confirmed that the preferred sequence of reaction steps involves reduction of the V(V) complex by phosphine, followed by condensation of the glycol into a [VO(dipic)(-O-CH2CH2-O-)] V(III) complex (6), which then evolves to the alkene product, with recovery of the catalyst. In contrast to the usually invoked closed-shell mechanism for the latter steps, where 6 suffers a [3+2] retrocycloaddition, we have found that the homolytic cleavage of one of the C-O bonds in 6 is preferred by 12 kcal/mol. The resulting diradical intermediate then collapses to a metallacycle that evolves to the product through an aromatic [2+2] retrocycloaddition. We use this key change in the mechanism to propose ways to design better catalysts for this transformation. The analysis of the mechanisms in both singlet and triplet potential energy surfaces, together with the location of the MECPs between them, showcases this reaction as an interesting example of two-state reactivity. © 2016 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Rational Design in Catalysis: A Mechanistic Study of β-Hydride Eliminations in Gold(I) and Gold(III) Complexes Based on Features of the Reaction Valley.\n \n \n \n\n\n \n Castiñeira Reis, M.; López, C.; Kraka, E.; Cremer, D.; and Faza, O.\n\n\n \n\n\n\n Inorganic Chemistry, 55(17): 8636-8645. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{CastineiraReis20168636,\nauthor={Castiñeira Reis, M. and López, C.S. and Kraka, E. and Cremer, D. and Faza, O.N.},\ntitle={Rational Design in Catalysis: A Mechanistic Study of β-Hydride Eliminations in Gold(I) and Gold(III) Complexes Based on Features of the Reaction Valley},\njournal={Inorganic Chemistry},\nyear={2016},\nvolume={55},\nnumber={17},\npages={8636-8645},\ndoi={10.1021/acs.inorgchem.6b01188},\nabstract={β-Hydride eliminations for ethylgold(III) dichloride complexes are identified as reactions with an unusually long prechemical stage corresponding to the conformational preparation of the reaction complex and spanning six phases. The prechemical process is characterized by a geared rotation of the L-Au-L group (L = Cl) driving methyl group rotation and causing a repositioning of the ligands. This requires more than 28 kcal/mol of the total barrier of 34.0 kcal/mol, according to the unified reaction valley approach, which also determines that the energy requirements of the actual chemical process leading to the β-elimination product are only about 5.5 kcal/mol. A detailed mechanistic analysis was used as a basis for a rational design of substrates (via substituents on the ethyl group) and/or ligands, which can significantly reduce the reaction barrier. This strategy takes advantage of either a higher trans activity of the ligands or a tuned electronic demand of the ethyl group. The β-hydride elimination of gold(I) was found to suffer from strong Coulomb and exchange repulsion when a positively charged hydrogen atom enforces a coordination position in a d10-configured gold atom, thus triggering an unassisted σ-π AuI-C conversion. © 2016 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Copper-Catalyzed Skeletal Rearrangement of O-Propargyl Oximes: A Mechanistic Manifold.\n \n \n \n\n\n \n González Comesaña, M.; Nieto Faza, O.; Cid, M.; and Silva López, C.\n\n\n \n\n\n\n ChemCatChem, 8(16): 2696-2703. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{GonzalezComesana20162696,\nauthor={González Comesaña, M. and Nieto Faza, O. and Cid, M.M. and Silva López, C.},\ntitle={Copper-Catalyzed Skeletal Rearrangement of O-Propargyl Oximes: A Mechanistic Manifold},\njournal={ChemCatChem},\nyear={2016},\nvolume={8},\nnumber={16},\npages={2696-2703},\ndoi={10.1002/cctc.201600473},\nabstract={The Cu-mediated skeletal rearrangement of O-propargyl oximes features a mechanistic manifold that yields different compounds. Strategic modification of the substituent at the oxime moiety (R3) allows the selection of a preferred mechanistic route that leads to azete oxides/amidodienes (if R3 is an electron-poor/-rich aryl group) or to pyridine N-oxides (if R3 is an olefin). In the present work, we explore the mechanism that leads to each product. All the computed mechanisms have in common an initial stepwise 2,3-rearrangement that generates the key N-allenylnitrone intermediate the further reactivity of which will depend on the nature of the R3 substituent. Our calculations reveal the subtle details that govern the different behavior of this reaction with each of the aforementioned substituents and disclose a complex and multistep pathway to different aminodienes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n The Outer-Sphere Mechanism of Nitrene Transfer onto Gold(I) Alkyne Complexes.\n \n \n \n\n\n \n Costa, I.; Marín-Luna, M.; Comesaña, M.; Faza, O.; and Silva López, C.\n\n\n \n\n\n\n ChemCatChem, 8(14): 2387-2392. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Costa20162387,\nauthor={Costa, I. and Marín-Luna, M. and Comesaña, M.G. and Faza, O.N. and Silva López, C.},\ntitle={The Outer-Sphere Mechanism of Nitrene Transfer onto Gold(I) Alkyne Complexes},\njournal={ChemCatChem},\nyear={2016},\nvolume={8},\nnumber={14},\npages={2387-2392},\ndoi={10.1002/cctc.201600354},\nabstract={The recently developed nitrene transfer reaction onto gold-activated alkynes provides a route to safe and accessible synthons of α-diazo imides. This reaction is rather unique in that it requires AuI in catalytic amounts; however, this promiscuous metal is only used to activate the alkyne moiety. After such activation is obtained, the nitrene-transfer process occurs through an outer-sphere mechanism, in which the metal acts only as a spectator. Density functional theory was applied to elucidate this peculiar reaction and to provide a mechanistic explanation for the experimentally observed isomers at the double bond and imine sites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Submerged Barriers in the Ni+ Assisted Decomposition of Propionaldehyde.\n \n \n \n\n\n \n Mansell, A.; Theis, Z.; Gutierrez, M.; Faza, O.; Lopez, C.; and Bellert, D.\n\n\n \n\n\n\n Journal of Physical Chemistry A, 120(15): 2275-2284. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Mansell20162275,\nauthor={Mansell, A. and Theis, Z. and Gutierrez, M.G. and Faza, O.N. and Lopez, C.S. and Bellert, D.J.},\ntitle={Submerged Barriers in the Ni+ Assisted Decomposition of Propionaldehyde},\njournal={Journal of Physical Chemistry A},\nyear={2016},\nvolume={120},\nnumber={15},\npages={2275-2284},\ndoi={10.1021/acs.jpca.5b08444},\nabstract={The reaction dynamics of the Ni+ mediated decarbonylation of propionaldehyde was assessed using the single photon initiated decomposition rearrangement reaction (SPIDRR) technique. The exothermic production of Ni+CO was temporally monitored and the associated rate constants, k(E), were extracted as a function of activating photon energy. In addition, the reaction potential energy surface was calculated at the UCCSD(T)/def2-TZVP//PBEPBE/cc-pVDZ level of theory to provide an atomistic description of the reaction profile. The decarbonylation of propionaldehyde can be understood as proceeding through parallel competitive reaction pathways that are initiated by Ni+ insertion into either the C-C or C-H bond of the propionaldehyde carbonyl carbon. Both paths lead to the elimination of neutral ethane and are governed by submerged barriers. The lower energy sequence is a consecutive C-C/C-H addition process with a submerged barrier of 14 350 ± 600 cm-1. The higher energy sequence is a consecutive C-H/C-C addition process with a submerged barrier of 15 400 ± 600 cm-1. Both barriers were determined using RRKM calculations fit to the experimentally determined k(E) values. The measured energy difference between the two barriers agrees with the DFT computed difference in rate limiting transition-state energies, 18 413 and 19 495 cm-1. © 2016 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Solving the Pericyclic-Pseudopericyclic Puzzle in the Ring-Closure Reactions of 1,2,4,6-Heptatetraene Derivatives.\n \n \n \n\n\n \n López, C.; Faza, O.; Freindorf, M.; Kraka, E.; and Cremer, D.\n\n\n \n\n\n\n Journal of Organic Chemistry, 81(2): 404-414. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez2016404,\nauthor={López, C.S. and Faza, O.N. and Freindorf, M. and Kraka, E. and Cremer, D.},\ntitle={Solving the Pericyclic-Pseudopericyclic Puzzle in the Ring-Closure Reactions of 1,2,4,6-Heptatetraene Derivatives},\njournal={Journal of Organic Chemistry},\nyear={2016},\nvolume={81},\nnumber={2},\npages={404-414},\ndoi={10.1021/acs.joc.5b01997},\nabstract={The ongoing controversy whether cyclization reactions of conjugated allenes or ketenes follow a pericyclic or a pseudopericyclic mechanism has triggered dozens of investigations, which have led to new valuable synthetic routes. In this work, the mechanism of 10 representative cyclization reactions of hepta-1,2,4,6-tetraenes with different terminal groups is investigated utilizing the unified reaction valley approach that registers all electronic structure changes of the target molecule along the entire reaction pathway. A clear differentiation between a purely pericyclic and a purely pseudopericyclic mechanism is established. Additionally, it is found that, by using suitable functional groups, a pericyclic mechanism can be converted into a pseudopericyclic one, which is associated with a steady decrease of the reaction barrier and a continuous change from one mechanism to the other. The energetics of the reaction are confirmed by coupled cluster calculations of the CCSD(T) type. The mechanistic insight gained is used to design new pseudopericyclic reactions with low or no barrier, which will open new synthetic avenues. © 2015 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited.\n \n \n \n\n\n \n Velasco, R.; Silva López, C.; Nieto Faza, O.; and Sanz, R.\n\n\n \n\n\n\n Chemistry - A European Journal, 22(42): 15058-15068. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Velasco201615058,\nauthor={Velasco, R. and Silva López, C. and Nieto Faza, O. and Sanz, R.},\ntitle={Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited},\njournal={Chemistry - A European Journal},\nyear={2016},\nvolume={22},\nnumber={42},\npages={15058-15068},\ndoi={10.1002/chem.201602254},\nabstract={By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α-lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]-Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α-lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron-poor aryl groups that favor the anionic pathway. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Conformational control allows for [3,3]-sigmatropic rearrangements to proceed with torquoselectivity.\n \n \n \n\n\n \n López, R.; Faza, O.; and López, C.\n\n\n \n\n\n\n RSC Advances, 6(64): 59181-59184. 2016.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez201659181,\nauthor={López, R.V. and Faza, O.N. and López, C.S.},\ntitle={Conformational control allows for [3,3]-sigmatropic rearrangements to proceed with torquoselectivity},\njournal={RSC Advances},\nyear={2016},\nvolume={6},\nnumber={64},\npages={59181-59184},\ndoi={10.1039/c6ra10789c},\nabstract={The Woodward-Hoffmann rules determine a first level of selectivity in pericyclic reactions. In this framework torqueselectivity can be defined as an additional degree of selectivity in electrocyclizations favouring one of the two allowed pathways. In this communication we extend this second level of selectivity beyond electrocyclizations. We have designed substrates that undergo a [3,3]-sigmatropic rearrangement in a torqueselective fashion. This behaviour is conformation dependent and is only observed when the reaction proceeds via a boat transition state. Structural design aimed at conformational control at the transition state, ensuring a boat-like structure, provides the first example of a [3,3]-sigmatropic shift that occurs with torqueselectivity. © 2016 The Royal Society of Chemistry.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2015\n \n \n (4)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Accounting for Diradical Character through DFT. the Case of Vinyl Allene Oxide Rearrangement.\n \n \n \n\n\n \n López, R.; Faza, O.; and López, C.\n\n\n \n\n\n\n Journal of Organic Chemistry, 80(21): 11206-11211. 2015.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 2 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez201511206,\nauthor={López, R.V. and Faza, O.N. and López, C.S.},\ntitle={Accounting for Diradical Character through DFT. the Case of Vinyl Allene Oxide Rearrangement},\njournal={Journal of Organic Chemistry},\nyear={2015},\nvolume={80},\nnumber={21},\npages={11206-11211},\ndoi={10.1021/acs.joc.5b02072},\nabstract={The transformation of vinyl allene oxides into cyclopentenones is key to the biosynthesis of a number of hormone-like molecules in plants. Two competitive paths are generally accepted for this transformation: a concerted SN2-like mechanism and a stepwise path with a diradical oxyallyl intermediate. Recently, a new stepwise closed-shell path has been proposed that circumvents the key oxyallyl intermediate. In this work, we conduct a thorough computational investigation, including dynamic effects, to identify the most likely mechanism for this transformation. © 2015 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Brønsted Acid-Catalyzed Cascade Reactions Involving 1,2-Indole Migration.\n \n \n \n\n\n \n Álvarez, E.; Nieto Faza, O.; Silva Lõpez, C.; Fernández-Rodríguez, M.; and Sanz, R.\n\n\n \n\n\n\n Chemistry - A European Journal, 21(37): 12889-12893. 2015.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Alvarez201512889,\nauthor={Álvarez, E. and Nieto Faza, O. and Silva Lõpez, C. and Fernández-Rodríguez, M.A. and Sanz, R.},\ntitle={Brønsted Acid-Catalyzed Cascade Reactions Involving 1,2-Indole Migration},\njournal={Chemistry - A European Journal},\nyear={2015},\nvolume={21},\nnumber={37},\npages={12889-12893},\ndoi={10.1002/chem.201502174},\nabstract={A cascade reaction of indoles with propargylic diols involving an unprecedented metal-free 1,2-indole migration onto an alkyne was carried out. DFT calculations support a mechanism consisting of a concerted nucleophilic attack of the indole nucleus with loss of water, followed by the 1,2-migration and subsequent Nazarov cyclization. This Brønsted acid-catalyzed protocol affords indole-functionalized benzofulvene derivatives in high yields. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Opening access to new chiral macrocycles: From allenes to spiranes.\n \n \n \n\n\n \n Castro-Fernández, S.; Cid, M.; López, C.; and Alonso-Gómez, J.\n\n\n \n\n\n\n Journal of Physical Chemistry A, 119(9): 1747-1753. 2015.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Castro-Fernandez20151747,\nauthor={Castro-Fernández, S. and Cid, M.M. and López, C.S. and Alonso-Gómez, J.L.},\ntitle={Opening access to new chiral macrocycles: From allenes to spiranes},\njournal={Journal of Physical Chemistry A},\nyear={2015},\nvolume={119},\nnumber={9},\npages={1747-1753},\ndoi={10.1021/jp508414r},\nabstract={Chiral macrocycles offer great potential and versatility regarding their applications. They have been employed in asymmetric catalysts, as chiral sensors, and as chiral supramolecular frameworks. For these reasons, they have been attracting increasing interest over the years. Despite all of the work developed in this area, most of the reported chiral macrocycles are not conformationally stable and present weak chiroptical responses. Such features substantially limit the scope of applications for these compounds. On the other hand, we have shown that axially chiral allenes can be introduced into macrocycles, conferring conformational stability and outstanding chiroptical responses. However, these allenes photoisomerize when conjugated with electron-donating groups, hampering the possibility of synthesizing systems with tuned optical properties. To overcome all of these limitations with a single structural motif, we propose the use of spiranes to construct new stable, conformationally rigid, and chemically functionalizable macrocyclic structures with strong chiroptical responses. As a first step in this new direction, we theoretically predict the chiroptical responses for macrocycles bearing spiranes to be as strong as with their allenic counterparts. As a side product, we also test the popular Minnesota functional, M06-2X, and compare it with cam-B3LYP, which has been previously analyzed with respect to experimental data in our laboratory. Thus, we hereby propose that spiranes are a good alternative to allenes for the construction of new chiral macrocycles. © 2014 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Diradical ring closing reactions displaying Woodward-Hoffmann behaviour and torquoselectivity.\n \n \n \n\n\n \n Villar López, R.; Nieto Faza, O.; and Silva López, C.\n\n\n \n\n\n\n RSC Advances, 5(38): 30405-30408. 2015.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{VillarLopez201530405,\nauthor={Villar López, R. and Nieto Faza, O. and Silva López, C.},\ntitle={Diradical ring closing reactions displaying Woodward-Hoffmann behaviour and torquoselectivity},\njournal={RSC Advances},\nyear={2015},\nvolume={5},\nnumber={38},\npages={30405-30408},\ndoi={10.1039/c5ra01742d},\nabstract={The symmetry rules enunciated in 1965 by Woodward and Hoffmann govern pericyclic reactions. They have been successfully applied to a wealth of concerted reactions showing exceptional predictive power and control. In this communication, we present evidence of reminiscent orbital control, analogue to that described by Woodward-Hoffmann (WH), dictating the course of diradical reactions. In this regard, the frontiers of application of these symmetry rules may be broader than what is commonly recognized. This journal is © The Royal Society of Chemistry.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2014\n \n \n (1)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Computational approaches to homogeneous gold catalysis.\n \n \n \n\n\n \n Faza, O.; and López, C.\n\n\n \n\n\n\n Topics in Current Chemistry, 357: 213-284. 2014.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 5 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza2014213,\nauthor={Faza, O.N. and López, C.S.},\ntitle={Computational approaches to homogeneous gold catalysis},\njournal={Topics in Current Chemistry},\nyear={2014},\nvolume={357},\npages={213-284},\ndoi={10.1007/128_2014_591},\nabstract={Homogenous gold catalysis has been exploding for the last decade at an outstanding pace. The best described reactivity of Au(I) and Au(III) species is based on gold’s properties as a soft Lewis acid, but new reactivity patterns have recently emerged which further expand the range of transformations achievable using gold catalysis, with examples of dual gold activation, hydrogenation reactions, or Au(I)/ Au(III) catalytic cycles. In this scenario, to develop fully all these new possibilities, the use of computational tools to understand at an atomistic level of detail the complete role of gold as a catalyst is unavoidable. In this work we aim to provide a comprehensive review of the available benchmark works on methodological options to study homogenous gold catalysis in the hope that this effort can help guide the choice of method in future mechanistic studies involving gold complexes. This is relevant because a representative number of current mechanistic studies still use methods which have been reported as inappropriate and dangerously inaccurate for this chemistry. Together with this, we describe a number of recent mechanistic studies where computational chemistry has provided relevant insights into non-conventional reaction paths, unexpected selectivities or novel reactivity, which illustrate the complexity behind gold-mediated organic chemistry. © Springer International Publishing Switzerland 2014.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2013\n \n \n (4)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Bis(o-methylserotonin)-containing iridium(III) and ruthenium(II) complexes as new cellular imaging dyes: Synthesis, applications, and photophysical and computational studies.\n \n \n \n\n\n \n Núñez, C.; Silva López, C.; Faza, O.; Fernández-Lodeiro, J.; Diniz, M.; Bastida, R.; Capelo, J.; and Lodeiro, C.\n\n\n \n\n\n\n Journal of Biological Inorganic Chemistry, 18(6): 679-692. 2013.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Nunez2013679,\nauthor={Núñez, C. and Silva López, C. and Faza, O.N. and Fernández-Lodeiro, J. and Diniz, M. and Bastida, R. and Capelo, J.L. and Lodeiro, C.},\ntitle={Bis(o-methylserotonin)-containing iridium(III) and ruthenium(II) complexes as new cellular imaging dyes: Synthesis, applications, and photophysical and computational studies},\njournal={Journal of Biological Inorganic Chemistry},\nyear={2013},\nvolume={18},\nnumber={6},\npages={679-692},\ndoi={10.1007/s00775-013-1013-5},\nabstract={We report the synthesis, characterization, and scope of a new versatile emissive molecular probe functionalized with a 1,10-phenanthroline moiety containing methylserotonin groups as binding sites for metal ion recognition. The synthesis, characterization, and evaluation of the in vitro imaging capability of the iridium(III) and ruthenium(II) complexes [Ir(ppy) 2(N-N)]+ and [Ru(bpy)2(N-N)]2+, in which ppy is 2-phenylpyridine, bpy is 2,2′-bipyridine, and N-N is a 1,10-phenanthroline ligand functionalized with two methylserotonin groups to serve as binding sites for metal ion recognition, is reported. The uptake of these compounds by living freshwater fish (Carassius auratus) was studied by fluorescence microscopy, and the cytotoxicity of ligand N-N and [Ru(bpy) 2(N-N)]2+ in this species was also investigated. Graphical abstract: [Figure not available: see fulltext.] © 2013 SBIC.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Noyori hydrogenation: Aromaticity, synchronicity, and activation strain analysis.\n \n \n \n\n\n \n Faza, O.; López, C.; and Fernández, I.\n\n\n \n\n\n\n Journal of Organic Chemistry, 78(11): 5669-5676. 2013.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza20135669,\nauthor={Faza, O.N. and López, C.S. and Fernández, I.},\ntitle={Noyori hydrogenation: Aromaticity, synchronicity, and activation strain analysis},\njournal={Journal of Organic Chemistry},\nyear={2013},\nvolume={78},\nnumber={11},\npages={5669-5676},\ndoi={10.1021/jo400837n},\nabstract={By means of density functional theory calculations, we have computationally explored the intimacies of the crucial step of Noyori hydrogrogenation reactions of multiple bonds. This process can be considered analogous to the so-called double group transfer reactions. Both kinds of transformations proceed concertedly via the simultaneous migration of two hydrogen atoms/groups in a pericyclic [σ2s + σ2s + π2s] reaction through six-membered transition structures. Despite the structural resemblances of both types of saddle points, significant differences are found in terms of synchronicity and in-plane aromaticity. In addition, the activation strain model has been used to get quantitative insight into the factors which control the corresponding barrier heights. It is found that the presence of a heteroatom in the acceptor moiety is responsible for a remarkable increase of the interaction energy between the reactants which can compensate the destabilizing effect of the strain energy associated with the deformation of the initial reagents leading to low reaction barriers. © 2013 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Computational study of gold-catalyzed homo- and cross-coupling reactions.\n \n \n \n\n\n \n Faza, O.; and López, C.\n\n\n \n\n\n\n Journal of Organic Chemistry, 78(10): 4929-4939. 2013.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza20134929,\nauthor={Faza, O.N. and López, C.S.},\ntitle={Computational study of gold-catalyzed homo- and cross-coupling reactions},\njournal={Journal of Organic Chemistry},\nyear={2013},\nvolume={78},\nnumber={10},\npages={4929-4939},\ndoi={10.1021/jo4005603},\nabstract={The role of gold as the organizing metal in homo- and cross-coupling reactions is explored in this paper combining DFT calculations with QTAIM, NBO, and the energetic span model analysis. For the gold(III) complex 7, a key intermediate in the experimental oxidative coupling scheme by Zhang et al., we describe the mechanisms corresponding to a cross-coupling after transmetalation with boron compounds and to a homocoupling after transmetalation with the original gold(I) complex 6, a new example of dual role of this metal in homogeneous catalysis. We predict for the first path a two-step transmetalation with a low energy rate-limiting step characterized by a four-center transition structure, where fluorine plays an essential role, followed by a reductive elimination where the C-C bond formation is coupled to the departure of fluorine from the gold center. The homocoupling path follows a similar mechanism, with a two-step transmetalation with interesting changes in bonding around the Au(I) center and a rate-limiting reductive elimination. Our findings on the competition between mechanisms, and the effect of ligands and solvent, agree with the experimental results and provide new insights into the mechanism of gold-catalyzed cross-coupling reactions. © 2013 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Computational insights on the mechanism of the catalytic hydrogenation with BINAP-diamine-Ru complexes: The role of base and origin of selectivity.\n \n \n \n\n\n \n Faza, O.; Fernández, I.; and López, C.\n\n\n \n\n\n\n Chemical Communications, 49(39): 4277-4279. 2013.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza20134277,\nauthor={Faza, O.N. and Fernández, I. and López, C.S.},\ntitle={Computational insights on the mechanism of the catalytic hydrogenation with BINAP-diamine-Ru complexes: The role of base and origin of selectivity},\njournal={Chemical Communications},\nyear={2013},\nvolume={49},\nnumber={39},\npages={4277-4279},\ndoi={10.1039/c2cc37165k},\nabstract={In this work we show that a base is needed to generate the active catalyst through any of three different paths close in energy. The facial differentiation arises from steric interactions that induce a very asynchronous, non-pericyclic disfavored transition state. Catalyst regeneration takes place through two steps that avoid a forbidden pericyclic mechanism. © 2013 The Royal Society of Chemistry.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2012\n \n \n (3)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Theoretical and experimental exploration of the photochemistry of resveratrol: Beyond the simple double bond isomerization.\n \n \n \n\n\n \n Rodríguez, R.; Lahoz, I.; Faza, O.; Cid, M.; and Lopez, C.\n\n\n \n\n\n\n Organic and Biomolecular Chemistry, 10(46): 9175-9182. 2012.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Rodriguez20129175,\nauthor={Rodríguez, R.Á. and Lahoz, I.R. and Faza, O.N. and Cid, M.M. and Lopez, C.S.},\ntitle={Theoretical and experimental exploration of the photochemistry of resveratrol: Beyond the simple double bond isomerization},\njournal={Organic and Biomolecular Chemistry},\nyear={2012},\nvolume={10},\nnumber={46},\npages={9175-9182},\ndoi={10.1039/c2ob26241j},\nabstract={The photochemical isomerization of resveratrol has been the subject of recent studies in which contradictory results were reported. The photoproduct mixture of this reaction needs to be considered more complex than the coexistence of cis and trans isomers. An unidentified third product, at least, has been detected in various studies although its nature was unknown. In this work, we aim to provide a thorough description of the photochemical course of this reaction through experimental and computational approaches working in a synergetic association. © 2012 The Royal Society of Chemistry.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n A stepwise retro-imino-ene as a key step in the mechanism of allene formation via the Crabbé acetylene homologation.\n \n \n \n\n\n \n González, M.; Rodríguez, R.; Cid, M.; and López, C.\n\n\n \n\n\n\n Journal of Computational Chemistry, 33(13): 1236-1239. 2012.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Gonzalez20121236,\nauthor={González, M. and Rodríguez, R.Á. and Cid, M.M. and López, C.S.},\ntitle={A stepwise retro-imino-ene as a key step in the mechanism of allene formation via the Crabbé acetylene homologation},\njournal={Journal of Computational Chemistry},\nyear={2012},\nvolume={33},\nnumber={13},\npages={1236-1239},\ndoi={10.1002/jcc.22954},\nabstract={The mechanism of the acetylene homologation procedure accidentally discovered and further developed by Crabbé and coworkers is unknown. Kinetic isotope effect (KIE) experiments, however, suggest that an intramolecular hydrogen shift is the key step of the transformation. In this work, we present a computational study of this mechanism. We found that the reaction proceeds via an unexpected stepwise retro-imino-ene rearrangement. This mechanism justifies the role of Cu(I) as a reaction catalyst and is also compatible with the KIE experiments reported. © 2012 Wiley Periodicals, Inc.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Novel emissive podands based on 8-OH-quinoline: Synthesis, fluorescence materials, DFT and complexation studies.\n \n \n \n\n\n \n Fernández-Lodeiro, J.; Núñez, C.; Nieto Faza, O.; Capelo, J.; Lodeiro, C.; Sérgio Seixas De Melo, J.; and López, C.\n\n\n \n\n\n\n Inorganica Chimica Acta, 381(1): 218-228. 2012.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Fernandez-Lodeiro2012218,\nauthor={Fernández-Lodeiro, J. and Núñez, C. and Nieto Faza, O. and Capelo, J.L. and Lodeiro, C. and Sérgio Seixas De Melo, J. and López, C.S.},\ntitle={Novel emissive podands based on 8-OH-quinoline: Synthesis, fluorescence materials, DFT and complexation studies},\njournal={Inorganica Chimica Acta},\nyear={2012},\nvolume={381},\nnumber={1},\npages={218-228},\ndoi={10.1016/j.ica.2011.09.018},\nabstract={Two novel chemosensors with podand structures (L 1 and L 2) derived from 1,5-bis(2-aminophenoxy)-3-oxopenthane bearing two flexible 8-hydroxyquinoline units have been synthesized and characterized. Several nitrate complexes of transition (Cu 2+), post-transition (Zn 2+) and lanthanide (Eu 3+ and Sm 3+) metal ions have been synthesized with tetrafluoroborate salts and characterized. In order to study their potential utility as fluorescent probes, the coordination ability of chemosensors (L 1 and L 2) towards those metal ions has been explored in solution (by UV-Vis and emission spectroscopy) and in gas phase (by MALDI mass spectrometry). Density functional theory has been employed to explore the emission properties of the three-protonation states of the chemosensor. From this study, the anomalous red shift observed in the fluorescence spectra of the dianionic sensors can be attributed to subtle structural differences between their anionic and dianionic forms. Furthermore, a plausible explanation for the low fluorescence of the neutral form is provided in the form of a non-radiative relaxation involving the imine double-bond isomerization. All new compounds have been characterized by microanalysis, melting points, IR, UV-Vis and fluorescence emission spectroscopy and MALDI-TOF-mass spectrometry. © 2011 Elsevier B.V. All rights reserved.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2011\n \n \n (6)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Bond ellipticity as a measure of electron delocalization in structure and reactivity.\n \n \n \n\n\n \n López, C.; and de Lera, A.\n\n\n \n\n\n\n Current Organic Chemistry, 15(20): 3576-3593. 2011.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20113576,\nauthor={López, C.S. and de Lera, A.R.},\ntitle={Bond ellipticity as a measure of electron delocalization in structure and reactivity},\njournal={Current Organic Chemistry},\nyear={2011},\nvolume={15},\nnumber={20},\npages={3576-3593},\ndoi={10.2174/138527211797636228},\nabstract={The ellipticity of the electron density at the bond critical points is a parameter computed in the framework of the Atoms in Molecules (AIM) analysis. This parameter provides a quantitative measurement of the anisotropy of the electron density at the BCP. The ellipticity has been originally associated to the φ character of bonds, and therefore, it has been also employed as a measurement of delocalization and, ultimately, aromaticity. The number of applications of this parameter, however, has increased significantly in recent years and studies on the description of unusual bonds in charge transfer interactions, steric contacts, organometallic complexes, etc include the ellipticity as a useful chemical index. In this work a revision of the uses of ellipticity to characterize both molecular bonds and reactivity is provided. © 2011 Bentham Science Publishers.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Computational study of the intramolecular pericyclic reactions of aldazines and some pseudopericyclic variants.\n \n \n \n\n\n \n González Pérez, A.; Souto, J.; Silva López, C.; and De Lera, A.\n\n\n \n\n\n\n European Journal of Organic Chemistry, (16): 2933-2939. 2011.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{GonzalezPerez20112933,\nauthor={González Pérez, A.B. and Souto, J.A. and Silva López, C. and De Lera, A.R.},\ntitle={Computational study of the intramolecular pericyclic reactions of aldazines and some pseudopericyclic variants},\njournal={European Journal of Organic Chemistry},\nyear={2011},\nnumber={16},\npages={2933-2939},\ndoi={10.1002/ejoc.201001737},\nabstract={The mechanisms of the complex cascade cyclizations of homoallenyl aldazines and analogues to afford tetracyclic compounds has been computed. Double sequential crisscross 1,3-dipolar cycloaddition through azomethine imine intermediates was characterized both for the homoallenyl aldazine and for its ketene analogue. If conjugation of the two interacting groups (azine and allene/ketene was introduced through the presence of an olefin system or an oxygen atom in place of the saturated carbon, pseudopericyclic mechanisms were also characterized. Unlike in the parent system, the barrierless cascade electrocyclization of [(Z)-hexa-2,4,5-trien-1-ylidene]hydrazine and of its ketene analogue is interrupted after formation of the 2,2′- methylenebis(dihydropyridine and bis-2,2′-pyridone, respectively, by pseudoelectrocyclic reactions. The cascade reaction of a hypothetical diazine with an allenylformimidate structure generates a compound containing four fused five-membered heterocyclic rings through a sequence that differs from that of the parent homoallenyl aldazine in the involvement of 6π-electron-5-atom electrocyclization and nucleophile-electrophile reaction steps before the final 1,3-dipolar cycloaddition. The analysis of the aromaticities of the transition structures through the computation of the NICS is consistent with their characterization as pericyclic or pseudopericyclic processes. Concerted but consecutive pericyclic and pseudopericyclic reactions have been characterized by DFT computations for crisscross 1,3-cycloaddition and electrocyclization reaction cascades of aldazines to provide complex tetracyclic derivatives containing up to four heteroatoms. © 2011 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n On the memory of chirality in gold(I)-catalyzed intramolecular carboalkoxylation of alkynes.\n \n \n \n\n\n \n Faza, O.; López, C.; and De Lera, A.\n\n\n \n\n\n\n Journal of Organic Chemistry, 76(10): 3791-3796. 2011.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza20113791,\nauthor={Faza, O.N. and López, C.S. and De Lera, A.R.},\ntitle={On the memory of chirality in gold(I)-catalyzed intramolecular carboalkoxylation of alkynes},\njournal={Journal of Organic Chemistry},\nyear={2011},\nvolume={76},\nnumber={10},\npages={3791-3796},\ndoi={10.1021/jo200090j},\nabstract={A computational study of the mechanism of the intramolecular carboalkoxylation of alkynes reported by Toste et al. allows the characterization of the chirality transfer process that makes this reaction enantioselective. Memory of chirality is preserved up until the stereocenter-generating iso-Nazarov cyclization through the synergy between the helicity of a pentadienyl cation intermediate and the control in the conformation of the allyl group, both elements defined upon alkoxy migration. The high barriers to conformational scrambling relative to those corresponding to chemical steps ensure the robustness of the chirality transfer mechanism and result in an unusual importance of conformational changes in reactivity that seems to be common in gold-catalyzed transformations. © 2011 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Experimental and computational exploration of indolizinyl carbene generation. A route to Biindolizines.\n \n \n \n\n\n \n Lahoz, I.; López, C.; Navarro-Vázquez, A.; and Cid, M.\n\n\n \n\n\n\n Journal of Organic Chemistry, 76(9): 3266-3273. 2011.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lahoz20113266,\nauthor={Lahoz, I.R. and López, C.S. and Navarro-Vázquez, A. and Cid, M.-M.},\ntitle={Experimental and computational exploration of indolizinyl carbene generation. A route to Biindolizines},\njournal={Journal of Organic Chemistry},\nyear={2011},\nvolume={76},\nnumber={9},\npages={3266-3273},\ndoi={10.1021/jo200157q},\nabstract={In previous work, (E)-2-enynyl pyridines were reported to yield indolizinyl singlet carbenes through base-catalyzed E/Z isomerization followed by a 5-exo-dig pseudocoarctate cyclization. We report herein that in the presence of ethyl acrylate these carbenes undergo stereoselective cis-cyclopropanation due mainly to electrostatic interactions in the transition state. The scope of this carbene generation scheme has been further explored through the preparation of a symmetric bis(pyridylenyl)alkyne which spontaneously furnished the biindolizine core in a one-pot reaction. Computational characterization of this transformation suggests a highly asynchronous double cyclization. © 2011 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Performance of density functional theory on homogeneous gold catalysis.\n \n \n \n\n\n \n Faza, O.; Rodríguez, R.; and López, C.\n\n\n \n\n\n\n Theoretical Chemistry Accounts, 128(4): 647-661. 2011.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 2 downloads\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza2011647,\nauthor={Faza, O.N. and Rodríguez, R.A. and López, C.S.},\ntitle={Performance of density functional theory on homogeneous gold catalysis},\njournal={Theoretical Chemistry Accounts},\nyear={2011},\nvolume={128},\nnumber={4},\npages={647-661},\ndoi={10.1007/s00214-010-0843-2},\nabstract={The performance of 32 density functionals to describe the homogeneous gold catalysis of propargyl esters has been tested. These catalytic reactions are very commonly rather complex, numerous intermediates can be found along the reaction profile and the individual reaction steps are often associated to very small barrier heights. In this scenario, the experimental kinetic study of the catalytic mechanisms is very challenging. A computational approach to this problem provides invaluable help to gain insight into these mechanisms. However the high accuracy needed to describe such highly branched paths with low energy transition states poses many practical problems for cost-efficient DFT methods. The lack of accurate experimental or high-level computational data to employ as validation sets for these methods is also an added difficulty. High-level computational data needed to validate these functionals have been obtained at the CCSD/def2-TZVPP//CCSD/def2-SVP level and, with such data, we aim to help discern the best density functional recipe for homogeneous gold catalysis © 2010 Springer-Verlag.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Novel versatile imine - Enamine chemosensor based on 6-nitro-4-oxo-4H- chromene for ion detection in solution, solid and gas-phase: Synthesis, emission, computational and MALDI-TOF-MS studies.\n \n \n \n\n\n \n Fernández-Lodeiro, J.; Nuñez, C.; Carreira, R.; Santos, H.; López, C.; Mejuto, J.; Capelo, J.; and Lodeiro, C.\n\n\n \n\n\n\n Tetrahedron, 67(2): 326-333. 2011.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Fernandez-Lodeiro2011326,\nauthor={Fernández-Lodeiro, J. and Nuñez, C. and Carreira, R. and Santos, H.M. and López, C.S. and Mejuto, J.C. and Capelo, J.L. and Lodeiro, C.},\ntitle={Novel versatile imine - Enamine chemosensor based on 6-nitro-4-oxo-4H- chromene for ion detection in solution, solid and gas-phase: Synthesis, emission, computational and MALDI-TOF-MS studies},\njournal={Tetrahedron},\nyear={2011},\nvolume={67},\nnumber={2},\npages={326-333},\ndoi={10.1016/j.tet.2010.11.040},\nabstract={A new versatile emissive molecular probe (3) derived from 1,5-bis(2-aminophenoxy)-3-oxopenthane bearing two units of 6-nitro-4-oxo-4H- chromene- has been prepared by a Schiff-base condensation method using conventional and green, ultrasound-aided, methods. The dry yellow powder was characterized as the imine species (3). These imine species, however, where found to rapidly convert to their enamine form (4) in solution, under the presence of water traces. This reaction was computationally studied through Density Functional Theory (DFT) in order to investigate the relative stability of the molecular pair 3/4. The sensing properties of the enamine (4) towards various metal ions were investigated via absorption and fluorometric titrations in solution in dichloromethane, acetonitrile and DMSO. The compound shows a fluorescent turn-off response in the presence of Cu2+, Zn 2+, Cd2+, Hg2+ and Ag+ over the other metal ions studied, such as Li+, Na+, K+, Ca2+, Co2+ and Ni2+, being stronger for Cu2+ and Hg2+. The gas phase chemosensing abilities of (3) were also explored suggesting (3) as new active MALDI-TOF-MS matrix by two dry methods showing a strong selectivity towards Cu2+ and Ag+. Our preliminary results show promising uses of (3) supported in PPMA films as metal ion solid chemosensor. Copyright © 2010 Published by Elsevier Ltd.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2010\n \n \n (3)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Molecular simulations in organic chemistry.\n \n \n \n\n\n \n Silva, C.\n\n\n \n\n\n\n Current Organic Chemistry, 14(15): 1523. 2010.\n \n\n\n\n
\n\n\n\n \n\n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Silva20101523,\nauthor={Silva, C.},\ntitle={Molecular simulations in organic chemistry},\njournal={Current Organic Chemistry},\nyear={2010},\nvolume={14},\nnumber={15},\npages={1523},\n}\n\n

\n

\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Cyclization cascade of allenyl azides: Synergy between theory and experiment.\n \n \n \n\n\n \n Faza, O.; Feldman, K.; and López, C.\n\n\n \n\n\n\n Current Organic Chemistry, 14(15): 1646-1657. 2010.\n \n\n\n\n
\n\n\n\n \n\n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza20101646,\nauthor={Faza, O.N. and Feldman, K.S. and López, C.S.},\ntitle={Cyclization cascade of allenyl azides: Synergy between theory and experiment},\njournal={Current Organic Chemistry},\nyear={2010},\nvolume={14},\nnumber={15},\npages={1646-1657},\nabstract={Collaborative work between experimentalists and computational chemists have demonstrated a stong synergy which allowed the rationalization of allenyl azide chemistry and permited the development of an efficient synthetic tool aimed at the preparation of several alkaloids. Saturated allenyl azides undergo a reaction cascade involving key diradical intermediates that follow the CurtinHammett model whereas unsaturated allenyl azides form indolidene intermediates that furnish the final indole products via electrocyclic ring closure events taking place out of the Curtin-Hammett regime. The regiochemistry of the reaction cascade with the latter substrates can be manipulated by Cu(I) addition to the reaction mixture. © 2010 Bentham Science Publishers Ltd.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Competing thermal electrocyclic ring-closure reactions of (2Z)-Hexa-2,4,5-trienals and their schiff bases. Structural, kinetic, and computational studies.\n \n \n \n\n\n \n Souto, J.; Pérez, M.; Silva López, C.; Álvarez, R.; Torrado, A.; and De Lera, A.\n\n\n \n\n\n\n Journal of Organic Chemistry, 75(13): 4453-4462. 2010.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Souto20104453,\nauthor={Souto, J.A. and Pérez, M. and Silva López, C. and Álvarez, R. and Torrado, A. and De Lera, A.R.},\ntitle={Competing thermal electrocyclic ring-closure reactions of (2Z)-Hexa-2,4,5-trienals and their schiff bases. Structural, kinetic, and computational studies},\njournal={Journal of Organic Chemistry},\nyear={2010},\nvolume={75},\nnumber={13},\npages={4453-4462},\ndoi={10.1021/jo100558p},\nabstract={(Figure presented) The electrocyclic ring closure reactions of (2Z)-hexa-2,4,5-trienals (vinylallenals) to alkylidene-2H-pyrans and of the corresponding Schiff base derivatives to alkylidenepyridines can be concurrent. Rates of vinylallenal cyclization and imine formation upon addition of n-butylamine determine the extent of the competition. The activation energies for the electrocyclization of a series of 6-substituted-(2Z)-4-tert-butyl-3- methylhexa-2,4,5-trienals 2 and trienimines 4 depend on the steric interactions between the substituents at C6 and the tert-butyl group at C4. Mixtures of alkylidene-2H-pyrans 3 and alkylidenepyridines 5 are obtained with bulky groups at C6, whereas only the latter is obtained with a C6-t-Bu and only the former with substituents of moderate size at C6. The reaction rates were indirectly derived from the empirical observations using a global optimization study based on differential evolution. The cyclizations are torquoselective, and the kinetically favored (E)-alkylidene heterocycles evolve by electrocyclic ring opening/ring closure toward the thermodynamic Z isomers upon extended reaction times. Density functional theory (DFT) calculations of the electrocyclizations helped in their characterization as monorotatory processes with pseudopericyclic features and made it possible to rationalize the reactivity trends and the torquoselectivity. © 2010 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2009\n \n \n (7)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Mechanistic investigation on the formation of indolizines from 2-enynylpyridines.\n \n \n \n\n\n \n Lahoz, I.; Sicre, C.; Navarro-Vázquez, A.; López, C.; and María-Magdalena, C.\n\n\n \n\n\n\n Organic Letters, 11(21): 4802-4805. 2009.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lahoz20094802,\nauthor={Lahoz, I.R. and Sicre, C. and Navarro-Vázquez, A. and López, C.S. and María-Magdalena, C.},\ntitle={Mechanistic investigation on the formation of indolizines from 2-enynylpyridines},\njournal={Organic Letters},\nyear={2009},\nvolume={11},\nnumber={21},\npages={4802-4805},\ndoi={10.1021/ol901760a},\nabstract={2,3,7-Trisubstituted Indolizines were obtained from E- or Z-2-enynyl-4-substltuted pyridines. The mechanistic pathway Involves a base-catalyzed double-bond Isomerlzatlon, If the E-lsomer Is the starting material, followed by a concerted pseudocoarctate cycllzatlon. © 2009 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Allenyl azide cycloaddition chemistry. 2,3-Cyclopentennelated indole synthesis through indolidene intermediates.\n \n \n \n\n\n \n Feldman, K.; Hester II, D.; Iyer, M.; Munson, P.; López, C.; and Faza, O.\n\n\n \n\n\n\n Journal of Organic Chemistry, 74(14): 4958-4974. 2009.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Feldman20094958,\nauthor={Feldman, K.S. and Hester II, D.K. and Iyer, M.R. and Munson, P.J. and López, C.S. and Faza, O.N.},\ntitle={Allenyl azide cycloaddition chemistry. 2,3-Cyclopentennelated indole synthesis through indolidene intermediates},\njournal={Journal of Organic Chemistry},\nyear={2009},\nvolume={74},\nnumber={14},\npages={4958-4974},\ndoi={10.1021/jo900659w},\nabstract={(Chemical Equation Presented) The thermal, photochemical, and photochemical/CuI-mediated cascade cyclizations of a range of substituted 1-(2-azidophenyl)-3-alkenylallenes are described. These reactions provide both 1,2- and 2,3-cyclopentennelated indole products in varying ratios. In most cases, high regioselectivity for the 2,3-annelated isomer can be achieved under the h?/CuI conditions. Computational studies of this multistep reaction support the intermediacy of indolidene intermediates whose electrocyclizations (with or without copper present) define the regioselectivity branch point in the sequence. © 2009 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Torquoselectivity in the electrocyclic ring-opening of cyclopropyl anions.\n \n \n \n\n\n \n Faza, O.; López, C.; González-Pérez, A.; Pérez-Rodríguez, M.; and De Lera, A.\n\n\n \n\n\n\n Journal of Physical Organic Chemistry, 22(5): 378-385. 2009.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza2009378,\nauthor={Faza, O.N. and López, C.S. and González-Pérez, A.B. and Pérez-Rodríguez, M. and De Lera, A.R.},\ntitle={Torquoselectivity in the electrocyclic ring-opening of cyclopropyl anions},\njournal={Journal of Physical Organic Chemistry},\nyear={2009},\nvolume={22},\nnumber={5},\npages={378-385},\ndoi={10.1002/poc.1455},\nabstract={Ring-opening reactions of substituted cyclopropanes are a convenient synthetic method for the preparation of functionalized alkenes. The Woodward-Hoffmann-DePuy rule governs the selectivity of the cationic process, as exemplified by the solvolysis of substituted halocyclopropanes but, although the reaction has been studied in detail, the torquoselectivity in the ring-opening of cyclopropyl anions has never been addressed. In this work, we use DFT calculations to study the two Woodward-Hoffmann allowed ring-opening paths available to cyclopropyl anions with different substitution patterns. We find that the reaction proceeds with torquoselectivity, evaluate the applicability of Houk's model to explain the effect of the substituents in the product distribution and correlate this effect with the aromaticity of the corresponding transition states. Copyright © 2008 John Wiley & Sons, Ltd.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Mechanism of the gold-catalyzed rearrangement of (3-acyloxyprop-1-ynyl) oxiranes: A dual role of the catalyst.\n \n \n \n\n\n \n Pérez, A.; López, C.; Marco-Contelles, J.; Faza, O.; Soriano, E.; and De Lera, A.\n\n\n \n\n\n\n Journal of Organic Chemistry, 74(8): 2982-2991. 2009.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Perez20092982,\nauthor={Pérez, A.G. and López, C.S. and Marco-Contelles, J. and Faza, O.N. and Soriano, E. and De Lera, A.R.},\ntitle={Mechanism of the gold-catalyzed rearrangement of (3-acyloxyprop-1-ynyl) oxiranes: A dual role of the catalyst},\njournal={Journal of Organic Chemistry},\nyear={2009},\nvolume={74},\nnumber={8},\npages={2982-2991},\ndoi={10.1021/jo802516k},\nabstract={The three competing paths for the rearrangement of 1 (involving 1,2- and 1,3-ester migration with alkyne or oxirane activation) evidence the multifaceted character of gold as a catalyst. The most favorable mechanism for this useful synthetic transformation involves a cascade of more than eight steps. All the functional groups in the substrate play a crucial and synergistic role, and sequential gold coordination to both the π-system and the lone pairs of oxygen is needed. Exploration of these three paths suggests the use of a nonalkynophilic Lewis acid (BF3) as a possible synthetic alternative for this transformation. © 2009 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Electrocyclic ring opening of charged cis-bicyclo[3.2.0]heptadiene and heterocyclic derivatives. the anti-Woodward-Hoffmann quest (II)1.\n \n \n \n\n\n \n López, C.; Faza, O.; and De Lera, Á.\n\n\n \n\n\n\n Journal of Organic Chemistry, 74(6): 2396-2402. 2009.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20092396,\nauthor={López, C.S. and Faza, O.N. and De Lera, Á.R.},\ntitle={Electrocyclic ring opening of charged cis-bicyclo[3.2.0]heptadiene and heterocyclic derivatives. the anti-Woodward-Hoffmann quest (II)1},\njournal={Journal of Organic Chemistry},\nyear={2009},\nvolume={74},\nnumber={6},\npages={2396-2402},\ndoi={10.1021/jo802678d},\nabstract={The ring opening reactions of fused cyclobutenes have been the subject of mechanistic debate for decades. Some reports have been published recently suggesting that, in some heterocyclic derivatives, the disrotatory anti-Woodward - Hoffmann mechanism might be responsible for the ring opening. We hereby show that the conrotatory pathway is still the lowest energy alternative for all cases examined, including push - pull substituted 2-thia-4-azabicyclo[3.2.0] hepta-3,6-dienes. Actually, we found that the disrotatory transition state exchanges roles with a double-bond isomerization depending on the substituents around the bicyclic structure. © 2009 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Regio-, peri-, and torquoselectivity in hydroxy heptatrienyl cation electrocyclizations: The iso/homo-nazarov reaction.\n \n \n \n\n\n \n Faza, O.; López, C.; Álvarez, R.; and De Lera, Á.\n\n\n \n\n\n\n Chemistry - A European Journal, 15(8): 1944-1956. 2009.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza20091944,\nauthor={Faza, O.N. and López, C.S. and Álvarez, R. and De Lera, Á.R.},\ntitle={Regio-, peri-, and torquoselectivity in hydroxy heptatrienyl cation electrocyclizations: The iso/homo-nazarov reaction},\njournal={Chemistry - A European Journal},\nyear={2009},\nvolume={15},\nnumber={8},\npages={1944-1956},\ndoi={10.1002/chem.200801133},\nabstract={The electrocyclizations of 1-and 3-hydroxyheptatrienyl cations have been computationally studied at the B3LYP/6-311G(d) level. The 1-hydroxy system clearly favors a 4πe- over a 6πe- process, while for the 3-hydroxy isomer these mechanisms compete. Substituents can either enhance or invert this periselectivity through steric or electronic effects, respectively. Houk's model of torquoselectivity helps to explain the activation energy differences between the alternative 4πe- electrocyclizations available for each system. The cyclopentenyl cations thus obtained can evolve, either through intramolecular trapping by the vinyl group or by 1,3-proton migration, along reaction coordinates which could correspond to either very asynchronous concerted mechanisms, or two-step reactions with very shallow or non-existent intermediates. © 2009 Wiley-VCH Verlag GmbH &amp; Co. KGaA.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Complex thermal behavior of 11-cis-retinal, the ligand of the visual pigments.\n \n \n \n\n\n \n López, C.; Álvarez, R.; Domínguez, M.; Faza, O.; and De Lera, A.\n\n\n \n\n\n\n Journal of Organic Chemistry, 74(3): 1007-1013. 2009.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20091007,\nauthor={López, C.S. and Álvarez, R. and Domínguez, M. and Faza, O.N. and De Lera, A.R.},\ntitle={Complex thermal behavior of 11-cis-retinal, the ligand of the visual pigments},\njournal={Journal of Organic Chemistry},\nyear={2009},\nvolume={74},\nnumber={3},\npages={1007-1013},\ndoi={10.1021/jo801899k},\nabstract={Upon heating to 80 °C, 11-cis-retinal yields a mixture of all-trans-retinal and 13-cis-retinal. This isomerization has been studied by means of density functional theory methods, and the computational results suggest a close competition between two mechanisms of very different nature. A classical internal rotation around the C11-C12 cis double bond, via a diradical transition state, accounts for the formation of the all-trans isomer. An intricate sequence of pericyclic reactions, namely a reversible [1,7]-H sigmatropic shift and a reversible 6-π-oxa-electrocyclic reaction, is responsible for the formation of 13-cis-retinal. Experiments using 11-cis-retinal labeled with deuterium at C19 confirmed the mechanistic proposal and also revealed an unprecedented outcome on the product composition of isotopologues. © 2009 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2008\n \n \n (5)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Allenyl azide cycloaddition chemistry: Exploration of the scope and mechanism of cyclopentennelated dihydropyrrole synthesis through azatrimethylenemethane intermediates.\n \n \n \n\n\n \n Feldman, K.; Iyer, M.; López, C.; and Faza, O.\n\n\n \n\n\n\n Journal of Organic Chemistry, 73(13): 5090-5099. 2008.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Feldman20085090,\nauthor={Feldman, K.S. and Iyer, M.R. and López, C.S. and Faza, O.N.},\ntitle={Allenyl azide cycloaddition chemistry: Exploration of the scope and mechanism of cyclopentennelated dihydropyrrole synthesis through azatrimethylenemethane intermediates},\njournal={Journal of Organic Chemistry},\nyear={2008},\nvolume={73},\nnumber={13},\npages={5090-5099},\ndoi={10.1021/jo8008066},\nabstract={(Chemical Equation Presented) Detailed studies of the thermal conversion of 1-azidohepta-3,4,6-trienes into cyclopentennelated dihydropyrroles are presented. High levels of diastereoselectivity and regioselectivity are documented. A mechanistic proposal that accounts for all of the diverse results is developed through the use of density functional calculations. These calculations provide support for the intervention of unexpected mechanistic subtleties, such as the planarity of an azatrimethylenemethane diyl intermediate and an apparent Woodward-Hoffmann-type electrocyclization of a five-atom diyl array. © 2008 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Allenl azide cycloaddtion chemistry. Photochemical initiation and cul mediation leads to improved regioselectivity.\n \n \n \n\n\n \n Feldman II, K.; Hester, D.; Lpez, C.; and Faza, O.\n\n\n \n\n\n\n Organic Letters, 10(8): 1665-1668. 2008.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{FeldmanII20081665,\nauthor={Feldman II, K.S. and Hester, D.K. and Lpez, C.S. and Faza, O.N.},\ntitle={Allenl azide cycloaddtion chemistry. Photochemical initiation and cul mediation leads to improved regioselectivity},\njournal={Organic Letters},\nyear={2008},\nvolume={10},\nnumber={8},\npages={1665-1668},\ndoi={10.1021/ol800429j},\nabstract={Irradiation of 2-(3-alkenyl)allenylphenyl azides in the presence of excess Cul furnished functionalized 2,3-cyclopentenylindoles in good yield with only trace amounts of competitive C-N-bonded regioisomeric products. These results represent a significant departure from the modest to-nonexistent regioselectivity that attended thermal cyclization of these allenyl azide substrates. © 2008 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Role of Mg2+ in hammerhead ribozyme catalysis from molecular simulation.\n \n \n \n\n\n \n Lee, T.; López, C.; Giambaşu, G.; Martick, M.; Scott, W.; and York, D.\n\n\n \n\n\n\n Journal of the American Chemical Society, 130(10): 3053-3064. 2008.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lee20083053,\nauthor={Lee, T.-S. and López, C.S. and Giambaşu, G.M. and Martick, M. and Scott, W.G. and York, D.M.},\ntitle={Role of Mg2+ in hammerhead ribozyme catalysis from molecular simulation},\njournal={Journal of the American Chemical Society},\nyear={2008},\nvolume={130},\nnumber={10},\npages={3053-3064},\ndoi={10.1021/ja076529e},\nabstract={Molecular dynamics simulations have been performed to investigate the role of Mg2+ in the full-length hammerhead ribozyme cleavage reaction. In particular, the aim of this work is to characterize the binding mode and conformational events that give rise to catalytically active conformations and stabilization of the transition state. Toward this end, a series of eight 12 ns molecular dynamics simulations have been performed with different divalent metal binding occupations for the reactant, early and late transition state using recently developed force field parameters for metal ions and reactive intermediates in RNA catalysis. In addition, hybrid QM/MM calculations of the early and late transition state were performed to study the proton-transfer step in general acid catalysis that is facilitated by the catalytic Mg2+ ion. The simulations suggest that Mg2+ is profoundly involved in the hammerhead ribozyme mechanism both at structural and catalytic levels. Binding of Mg2+ in the active site plays a key structural role in the stabilization of stem I and II and to facilitate formation of near attack conformations and interactions between the nucleophile and G12, the implicated general base catalyst. In the transition state, Mg2+ binds in a bridging position where it stabilizes the accumulated charge of the leaving group while interacting with the 2′OH of G8, the implicated general acid catalyst. The QM/MM simulations provide support that, in the late transition state, the 2′OH of G8 can transfer a proton to the leaving group while directly coordinating the bridging Mg2+ ion. The present study provides evidence for the role of Mg2+ in hammerhead ribozyme catalysis. The proposed simulation model reconciles the interpretation of available experimental structural and biochemical data, and provides a starting point for more detailed investigation of the chemical reaction path with combined QM/MM methods. © 2008 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Characterization of the switch in the mechanism of an intramolecular Diels-Alder reaction.\n \n \n \n\n\n \n López, C.; Faza, O.; and De Lera, A.\n\n\n \n\n\n\n Journal of Organic Chemistry, 73(2): 467-473. 2008.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez2008467,\nauthor={López, C.S. and Faza, O.N. and De Lera, A.R.},\ntitle={Characterization of the switch in the mechanism of an intramolecular Diels-Alder reaction},\njournal={Journal of Organic Chemistry},\nyear={2008},\nvolume={73},\nnumber={2},\npages={467-473},\ndoi={10.1021/jo701962t},\nabstract={(Chemical Equation Presented) Changing the dienophile moiety of an intramolecular Diels-Alder (IMDA) cycloaddition from an allyl ether to an allenyl ether can dramatically change the regioselectivity. We hereby show by density functional theory computations that such unprecedented divergence is produced by an underlying change in the mechanism of the reaction. The allyl ether yields a fused tetrahydrofuran through a classical Diels-Alder reaction, whereas the allenyl ether yields a (methylidene)tetrahydropyran through a stepwise process. The latter reaction involves an extreme asynchronism in the bond-forming events with a diradicaloid intermediate that is stabilized by conjugation and synergistic (captodative) effects. Comparison with intermolecular model D-A reactions, which are concerted processes with various degrees of asynchrony, helps explain the change in regioselectivity for the IMDA reaction of allyl systems and the shift in mechanism for the IMDA reaction of the allenyl derivatives studied. © 2008 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Mechanistic insights into the stereocontrolled synthesis of hexahydropyrrolo[2,3-b]indoles by electrophilic activation of tryptophan derivatives.\n \n \n \n\n\n \n López, C.; Pérez-Balado, C.; Rodríguez-Graña, P.; and De Lera, Á.\n\n\n \n\n\n\n Organic Letters, 10(1): 77-80. 2008.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez200877,\nauthor={López, C.S. and Pérez-Balado, C. and Rodríguez-Graña, P. and De Lera, Á.R.},\ntitle={Mechanistic insights into the stereocontrolled synthesis of hexahydropyrrolo[2,3-b]indoles by electrophilic activation of tryptophan derivatives},\njournal={Organic Letters},\nyear={2008},\nvolume={10},\nnumber={1},\npages={77-80},\ndoi={10.1021/ol702732j},\nabstract={A three-step mechanism involving the formation and rearrangement of an intermediate with indoline-azetidine spirocyclic core structure was shown by DFT computations to account for the electrophilic cyclization of tryptophan derivatives to hexahydropyrrolo[2,3-b]indoles. The corresponding 3a-bromo derivatives have been obtained in high yields and synthetically useful exolendo ratios. © 2008 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2007\n \n \n (5)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Cyclization cascade of allenyl azides: A dual mechanism.\n \n \n \n\n\n \n López, C.; Faza, O.; Feldman, K.; Iyer, M.; and Hester, D.\n\n\n \n\n\n\n Journal of the American Chemical Society, 129(24): 7638-7646. 2007.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20077638,\nauthor={López, C.S. and Faza, O.N. and Feldman, K.S. and Iyer, M.R. and Hester, D.K.},\ntitle={Cyclization cascade of allenyl azides: A dual mechanism},\njournal={Journal of the American Chemical Society},\nyear={2007},\nvolume={129},\nnumber={24},\npages={7638-7646},\ndoi={10.1021/ja070818l},\nabstract={A density functional theory based computational approach to describing the mechanistic course of the allene azide cycloaddition cascade sequence has been developed. The results of these calculations permit characterization of key reactive intermediates (diradicals and/or indolidenes) and explain the different behaviors observed in the experimental studies between conjugated and nonconjugated species. Furthermore, computational analysis of certain intermediates offer insight into issues of regioselectivity and stereoselectivity in cases where different reaction channels are in competition, suggesting suitable substitutions to achieve a single regioisomer in the indole synthesis via azide-allene cyclization. © 2007 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Electrocyclic ring opening of cis-bicyclo[m.n.0]alkenes: The anti-woodward-hoffmann quest.\n \n \n \n\n\n \n López, C.; Faza, O.; and De Lera, Á.\n\n\n \n\n\n\n Chemistry - A European Journal, 13(17): 5009-5017. 2007.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20075009,\nauthor={López, C.S. and Faza, O.N. and De Lera, Á.R.},\ntitle={Electrocyclic ring opening of cis-bicyclo[m.n.0]alkenes: The anti-woodward-hoffmann quest},\njournal={Chemistry - A European Journal},\nyear={2007},\nvolume={13},\nnumber={17},\npages={5009-5017},\ndoi={10.1002/chem.200601151},\nabstract={The dubbed anti-Woodward-Hoffmann ring-opening reaction of cis-bicyclo[4.2.0]oct-7-ene to yield cis,cis-cycloocta-1,3-diene has been intensively studied with robust, high-level computational methods. This reaction has been found to proceed through a conrotatory allowed pathway to afford cis,-trans-cycloocta-1,3-diene followed by E to Z isomerization, instead of a disrotatory forbidden pathway, as suggested. Computational calculations of kinetic isotope effects are consistent with this interpretation and the experimental values. The study of lower bicyclic homologues with [3.2.0], [2.2.0] and [2.1.0] skeletons indicates the feasibility of a mechanistic change towards the anti-Woodward-Hoffmann disrotatory path. This is clearly favored for the ring opening of the highly strained cis-bicyclo[2.1.0]pent-2-ene and is highly competitive with the conrotatory path for cis-bicyclo[2.2.0]hex-2-ene. Therefore, the rearrangement of the smallest bicyclic cyclobutene is predicted computationally to be an anti-Woodward-Hoffmann disrotatory electrocyclic ring-opening reaction. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Pseudopericyclic design drives antara-antara [1,5] methylene sigmatropic shifts from a stepwise to a concerted mechanism.\n \n \n \n\n\n \n López, C.; Faza, O.; Souto, J.; Álvarez, R.; and De Lera, Á.\n\n\n \n\n\n\n Journal of Computational Chemistry, 28(8): 1411-1416. 2007.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20071411,\nauthor={López, C.S. and Faza, O.N. and Souto, J.A. and Álvarez, R. and De Lera, Á.R.},\ntitle={Pseudopericyclic design drives antara-antara [1,5] methylene sigmatropic shifts from a stepwise to a concerted mechanism},\njournal={Journal of Computational Chemistry},\nyear={2007},\nvolume={28},\nnumber={8},\npages={1411-1416},\ndoi={10.1002/jcc.20620},\nabstract={Antara-antara [1,5]-methylene sigmatropic shifts of propenylidene cyclopropane and its heteroanalogues are shown to proceed through concerted or stepwise mechanisms depending on a delicate balance that is directly related to the presence or absence of heteroatoms at the termini atoms of the rearrangement. Lowering of activation energies upon heteroatom replacement are more significant for the oxacyclopropane analogues 1D, 1E, and 1F but double heterosubstitution is still needed to achieve a pseudopericyclic reaction. In fact only after reaching a pseudopericyclic process the energy balance favors the concerted pathway. Negligible NICS values and a clear disconnection in the ACID plot as well as some structural and energetical parameters reveal the pseudopericyclic nature of this concerted antara-antara [1,5]CH2 sigmatropic shift. Although the product of the pseudopericyclic process is unprecedented, similar cycloisomerizations after allene activation should be considered within this hitherto undescribed reactions. © 2007 Wiley Periodicals, Inc.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Sulfoxide-induced stereoselection in [1,5]-sigmatropic hydrogen shifts of vinylallenes. A computational study.\n \n \n \n\n\n \n Faza, O.; López, C.; and De Lera, A.\n\n\n \n\n\n\n Journal of Organic Chemistry, 72(7): 2617-2624. 2007.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza20072617,\nauthor={Faza, O.N. and López, C.S. and De Lera, A.R.},\ntitle={Sulfoxide-induced stereoselection in [1,5]-sigmatropic hydrogen shifts of vinylallenes. A computational study},\njournal={Journal of Organic Chemistry},\nyear={2007},\nvolume={72},\nnumber={7},\npages={2617-2624},\ndoi={10.1021/jo070050n},\nabstract={The sulfoxide-induced preference for a migrating trajectory in the vinylallene [1,5]-H sigmatropic shift (resulting in stereodefined trienes in the conceptual equivalent of torquoselectivity in electrocyclizations), originally reported by Okamura, has been computationally studied at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31++G(d,p) level. The face selectivity this group induces in the [1,5]-H shift is enhanced by bulky geminal substituents and is not reproduced by any of the other (more than 20) substituents tested. Analysis of transition-state geometries or charges and evaluation of steric effects did not show any correlation with the preferences. The origin of this selectivity is thought to lie in a secondary orbital interaction (SOI) involving the termini of the pericyclic array and the sulfinyl group which is only observed for this substituent. This secondary orbital interaction, arising from the favorable energies of the orbitals involved, is enhanced in the transition structure due to a better orbital overlap (πC2-C3 → σC1-S*), which correlates with a πC2-C3 → σC6-H* SOI, which is more important in the transition structure, that weakens the C-H bond, thus lowering the energy of the corresponding transition structure. © 2007 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Insight into the role of Mg2+ in hammerhead ribozyme catalysis from X-ray crystallography and molecular dynamics simulation.\n \n \n \n\n\n \n Lee, T.; Silva-López, C.; Martick, M.; Scott, W.; and York, D.\n\n\n \n\n\n\n Journal of Chemical Theory and Computation, 3(2): 325-327. 2007.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n \n \n 1 download\n \n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lee2007325,\nauthor={Lee, T.-S. and Silva-López, C. and Martick, M. and Scott, W.G. and York, D.M.},\ntitle={Insight into the role of Mg2+ in hammerhead ribozyme catalysis from X-ray crystallography and molecular dynamics simulation},\njournal={Journal of Chemical Theory and Computation},\nyear={2007},\nvolume={3},\nnumber={2},\npages={325-327},\ndoi={10.1021/ct6003142},\nabstract={Results of a series of 12 ns molecular dynamics (MD) simulations of the reactant state (with and without a Mg2+ ion) and early and late transition state mimics are presented based on a recently reported crystal structure of a full-length hammerhead RNA. The simulation results support a catalytically active conformation with a Mg2+ ion bridging the A9 and scissile phosphates. In the reactant state, the Mg2+ spends significant time closely associated with the 2′OH of G8 but remains fairly distant from the leaving group Q5′ position. In the early TS mimic simulation, where the nucteophilic O2′ and leaving group O5′ are equidistant from the phosphorus, the Mg2+ ion remains tightly coordinated to the 2′OH of G8 but is positioned closer to the O5′ leaving group, stabilizing the accumulating charge. In the late TS mimic simulation, the coordination around the bridging Mg 2+ ion undergoes a transition whereby the coordination with the 2′OH of G8 is replaced by the leaving group O5′ that has developed significant charge. At the same time, the 2′OH of G8 forms a hydrogen bond with the leaving group O5′ and is positioned to act as a general acid catalyst. This work represents the first reported simulations of the full-length hammerhead structure and TS mimics and provides direct evidence for the possible role of a bridging Mg2+ ion in catalysis that is consistent with both crystallographic and biochemical data. © 2007 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2006\n \n \n (7)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n QCRNA 1.0: A database of quantum calculations for RNA catalysis.\n \n \n \n\n\n \n Giese, T.; Gregersen, B.; Liu, Y.; Nam, K.; Mayaan, E.; Moser, A.; Range, K.; Faza, O.; Lopez, C.; Lera, A.; Schaftenaar, G.; Lopez, X.; Lee, T.; Karypis, G.; and York, D.\n\n\n \n\n\n\n Journal of Molecular Graphics and Modelling, 25(4): 423-433. 2006.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Giese2006423,\nauthor={Giese, T.J. and Gregersen, B.A. and Liu, Y. and Nam, K. and Mayaan, E. and Moser, A. and Range, K. and Faza, O.N. and Lopez, C.S. and Lera, A.R.d. and Schaftenaar, G. and Lopez, X. and Lee, T.-S. and Karypis, G. and York, D.M.},\ntitle={QCRNA 1.0: A database of quantum calculations for RNA catalysis},\njournal={Journal of Molecular Graphics and Modelling},\nyear={2006},\nvolume={25},\nnumber={4},\npages={423-433},\ndoi={10.1016/j.jmgm.2006.02.011},\nabstract={This work outlines a new on-line database of quantum calculations for RNA catalysis (QCRNA) available via the worldwide web at http://theory.chem.umn.edu/QCRNA. The database contains high-level density functional calculations for a large range of molecules, complexes and chemical mechanisms important to phosphoryl transfer reactions and RNA catalysis. Calculations are performed using a strict, consistent protocol such that a wealth of cross-comparisons can be made to elucidate meaningful trends in biological phosphate reactivity. Currently, around 2000 molecules have been collected in varying charge states in the gas phase and in solution. Solvation was treated with both the PCM and COSMO continuum solvation models. The data can be used to study important trends in reactivity of biological phosphates, or used as benchmark data for the design of new semiempirical quantum models for hybrid quantum mechanical/molecular mechanical simulations. © 2006 Elsevier Inc. All rights reserved.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Cycloisomerization of activated (2E,4Z)-heptatrienoate and its relevance to crispatene (bio)synthesis. A case of concerted and stepwise uncertainty.\n \n \n \n\n\n \n López, C.; Faza, O.; Álvarez, R.; and De Lera, Á.\n\n\n \n\n\n\n Journal of Organic Chemistry, 71(12): 4497-4501. 2006.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20064497,\nauthor={López, C.S. and Faza, O.N. and Álvarez, R. and De Lera, Á.R.},\ntitle={Cycloisomerization of activated (2E,4Z)-heptatrienoate and its relevance to crispatene (bio)synthesis. A case of concerted and stepwise uncertainty},\njournal={Journal of Organic Chemistry},\nyear={2006},\nvolume={71},\nnumber={12},\npages={4497-4501},\ndoi={10.1021/jo0603274},\nabstract={A single transition structure was located on the potential energy surface of the cycloisomerization of protic and Lewis acid activated (2E,4Z)-heptatrienal and the corresponding methyl ester to provide the bicyclo[3.1.0]hexene derivatives, the central skeleton of the crispatene natural products. A two-dimensional scan of the C-C bond-forming reactions revealed a barrierless cyclopropane closure following the pentadienyl cycloisomerization, with preservation of the stereochemical information. © 2006 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Computational study and analysis of the kinetic isotope effects of the rearrangement of cis-bicyclo[4.2.0]oct-7-ene to cis,cis-cycloocta-1,3-diene.\n \n \n \n\n\n \n López, C.; Faza, O.; and De Lera, Á.\n\n\n \n\n\n\n Organic Letters, 8(10): 2055-2058. 2006.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20062055,\nauthor={López, C.S. and Faza, O.N. and De Lera, Á.R.},\ntitle={Computational study and analysis of the kinetic isotope effects of the rearrangement of cis-bicyclo[4.2.0]oct-7-ene to cis,cis-cycloocta-1,3-diene},\njournal={Organic Letters},\nyear={2006},\nvolume={8},\nnumber={10},\npages={2055-2058},\ndoi={10.1021/ol060465f},\nabstract={On the basis of KIE experiments, the ring opening of cis-bicyclo[4.2.0.] oct-7-ene has been suggested as an anti-Woodward-Hoffmann reaction candidate. We hereby report the results of a high-level computational study of the alternate reaction pathways which proves that the energy profiles show a clear preference for the conrotatory (W-H allowed) ring opening followed by double-bond isomerization. Computed KIE values for the aforementioned mechanism are in good agreement with the experimental values. © 2006 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Mechanism of the gold(I)-catalyzed Rautenstrauch rearrangement: A center-to-helix-to-center chirality transfer.\n \n \n \n\n\n \n Nieto Faza, O.; Silva López, C.; Álvarez, R.; and De Lera, A.\n\n\n \n\n\n\n Journal of the American Chemical Society, 128(7): 2434-2437. 2006.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{NietoFaza20062434,\nauthor={Nieto Faza, O. and Silva López, C. and Álvarez, R. and De Lera, A.R.},\ntitle={Mechanism of the gold(I)-catalyzed Rautenstrauch rearrangement: A center-to-helix-to-center chirality transfer},\njournal={Journal of the American Chemical Society},\nyear={2006},\nvolume={128},\nnumber={7},\npages={2434-2437},\ndoi={10.1021/ja057127e},\nabstract={The mechanism of the stereospecific gold(I)-catalyzed Rautenstrauch rearrangement of (E)-1-ethynyl-2-methyl-but-2-en-yl acetate to 3,4-dimethyl-cyclopent-2-enone has been computationally addressed using DFT (B3LYP/6-31G*, SDD for Au). Our results indicate that the bond formation event follows the Au(I)-induced acetyl transfer to the vicinal alkyne and that it is the helicity of the pentadienyl cation intermediate which keeps memory of the chiral information. The fidelity of the center-to-helix-to-center chirality transfer requires that the rates of helix interconversion and pivaloyl rotation are slower than the cyclization, as calculations predict. © 2006 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Multilevel and density functional electronic structure calculations of proton affinities and gas-phase basicities involved in biological phosphoryl transfer.\n \n \n \n\n\n \n Range, K.; López, C.; Moser, A.; and York, D.\n\n\n \n\n\n\n Journal of Physical Chemistry A, 110(2): 791-797. 2006.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Range2006791,\nauthor={Range, K. and López, C.S. and Moser, A. and York, D.M.},\ntitle={Multilevel and density functional electronic structure calculations of proton affinities and gas-phase basicities involved in biological phosphoryl transfer},\njournal={Journal of Physical Chemistry A},\nyear={2006},\nvolume={110},\nnumber={2},\npages={791-797},\ndoi={10.1021/jp054360q},\nabstract={Five multilevel model chemistries (CBS-QB3, G3B3, G3MP2B3, MCG3/3, and MC-QCISD/3) and seven hybrid density functional methods (PBE0, B1B95, B3LYP, MPW1KCIS, PBE1KCIS, and MPW1B95) have been applied to the calculation of gas-phase basicity and proton affinity values for a series of 17 molecules relevant to the study of biological phosphoryl transfer. In addition, W1 calculations were performed on a subset of molecules. The accuracy of the methods was assessed and the nature of systematic errors was explored, leading to the introduction of a set of effective bond enthalpy and entropy correction terms. The multicoefficient correlation methods (MCG3/3 and MC-QCISD), with inclusion of specific zero-point scale factors, slightly outperform the other multilevel methods tested (CBS-QB3, G3B3, and G3MP2B3), with significantly less computational cost, and in the case of MC-QCISD, slightly less severe scaling. Four density functional methods, PBE1KCIS, MPW1B95, PBE0, and B1B95 perform nearly as well as the multilevel methods. These results provide an important set of benchmarks relevant to biological phosphoryl transfer reactions. © 2006 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Computation of vertical excitation energies of retinal and analogs: Scope and limitations.\n \n \n \n\n\n \n López, C.; Faza, O.; Estévez, S.; and De Lera, A.\n\n\n \n\n\n\n Journal of Computational Chemistry, 27(1): 116-123. 2006.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez2006116,\nauthor={López, C.S. and Faza, O.N. and Estévez, S.L. and De Lera, A.R.},\ntitle={Computation of vertical excitation energies of retinal and analogs: Scope and limitations},\njournal={Journal of Computational Chemistry},\nyear={2006},\nvolume={27},\nnumber={1},\npages={116-123},\ndoi={10.1002/jcc.20305},\nabstract={A comprehensive survey of computational methods: semiempirical (ZINDO/S), Time-Dependent HartreeFock (TD-HF), Configuration Interaction Singles (CIS), and several approximate functionals within the Time-Dependent Density Functional Theory (TD-DFT) has been carried out for the description of vertical excitation energies and oscillator strengths of retinal and related polyenals. ZINDO and TD-DFT computations showed the best agreement with the experimental data. In particular, hybrid functionals including approximately 25% of exact exchange (B3LYP, B3P86, and PBE0) were found to perform best with these highly conjugated polyenes. A systematic average error of 0.18-0.22 eV has been found after a simple one-parameter correction. Thus, 0.18 eV might be considered the upper limit of accuracy for current one-determinant methods in the computation of vertical excitation energies. The consideration of adiabatic excitations, conformational sampling, solvation, and nondynamic correlation should describe this processes more accurately, but this leads to highly demanding methods beyond feasibility for these large polyenes. The trends observed, particularly the good performance of the ZINDO/S method, should pave the way for the prediction of excited states properties in natural and artificial photoreceptor proteins, thus advancing towards the description of their light-transducing biological role in Nature. © 2005 Wiley Periodicals, Inc.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Computational characterization of a complete palladium-catalyzed cross-coupling process: The associative transmetalation in the Stille reaction.\n \n \n \n\n\n \n Álvarez, R.; Faza, O.; López, C.; and De Lera, Á.\n\n\n \n\n\n\n Organic Letters, 8(1): 35-38. 2006.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Alvarez200635,\nauthor={Álvarez, R. and Faza, O.N. and López, C.S. and De Lera, Á.R.},\ntitle={Computational characterization of a complete palladium-catalyzed cross-coupling process: The associative transmetalation in the Stille reaction},\njournal={Organic Letters},\nyear={2006},\nvolume={8},\nnumber={1},\npages={35-38},\ndoi={10.1021/ol052398f},\nabstract={(Chemical Equation Presented) The species presumably involved in the associative ligand substitution mechanism for the Stille cross coupling of vinyl bromide and trimethylvinyl stannane with Pd(PMe3) 2/PMe3 as catalysts in DMF (as ligand and solvent) have been structurally and energetically characterized. The cyclic four-coordinate transition state for the rate-determining transmetalation step explains the retention of configuration in the Stille coupling of chiral nonracemic alkyl stannanes. © 2006 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2005\n \n \n (6)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Synthesis of N-heteroaryl retinals and their artificial bacteriorhodopsins.\n \n \n \n\n\n \n López, S.; Rodríguez, V.; Montenegro, J.; Saá, C.; Alvarez, R.; Silva López, C.; De Lera, A.; Simón, R.; Lazarova, T.; and Padrós, E.\n\n\n \n\n\n\n ChemBioChem, 6(11): 2078-2087. 2005.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20052078,\nauthor={López, S. and Rodríguez, V. and Montenegro, J. and Saá, C. and Alvarez, R. and Silva López, C. and De Lera, A.R. and Simón, R. and Lazarova, T. and Padrós, E.},\ntitle={Synthesis of N-heteroaryl retinals and their artificial bacteriorhodopsins},\njournal={ChemBioChem},\nyear={2005},\nvolume={6},\nnumber={11},\npages={2078-2087},\ndoi={10.1002/cbic.200500148},\nabstract={N-Heteroaryl retinals derived from indole, 1-indolizine and 3-indolizine (10a-c) have been synthesized after their UV/Vis red-shifted absorption properties had been predicted by time-dependent density functional theory (TD-DFT) computations. The three new analogues form artificial pigments upon recombination with bacterioopsin: indolyl retinal 10a undergoes fast and efficient reconstitution to form a species with a UV/Vis absorbance maximum similar to that of wild-type bacteriorhodopsin, whilst the indolizinyl retinals 10b and 10c also reconstitute in significant proportion to give noticeably red-shifted, although unstable, pigments. Significant changes in the pK a values of these artificial bacteriorhodopsins are interpreted as arising from nonoptimal binding-site occupancy by the chromophore due to steric constraints. © 2005 Wiley-VCH Verlag GmbH &amp; Co. KGaA.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Mechanistic subtleties in the cyclopentannelation of allenolate allyl carbamates: The origin of the center-to-center chirality transfer.\n \n \n \n\n\n \n Faza, O.; López, C.; Álvarez, R.; and De Lera, Á.\n\n\n \n\n\n\n Chemical Communications, (34): 4285-4287. 2005.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza20054285,\nauthor={Faza, O.N. and López, C.S. and Álvarez, R. and De Lera, Á.R.},\ntitle={Mechanistic subtleties in the cyclopentannelation of allenolate allyl carbamates: The origin of the center-to-center chirality transfer},\njournal={Chemical Communications},\nyear={2005},\nnumber={34},\npages={4285-4287},\ndoi={10.1039/b506601h},\nabstract={The stereospecific rearrangement of allene carbamates i to alkylidenecyclopentenones iii is concerted, displays charge donation from the π*allenonate to the σ* C-leaving group, and shows mechanistic features of both pericyclic and ionic processes, modulated in part by the degree of ionic interaction (O-...Li+) in the putative intermediate allenolate ii. © The Royal Society of Chemistry 2005.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Simple diastereoselectivity of the BF3·OEt 2-catalyzed vinylogous Mukaiyama aldol reaction of 2-(trimethylsiloxy)furans with aldehydes.\n \n \n \n\n\n \n Lopez, C.; Álvarez, R.; Vaz, B.; Faza, O.; and De Lera, Á.\n\n\n \n\n\n\n Journal of Organic Chemistry, 70(9): 3654-3659. 2005.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20053654,\nauthor={Lopez, C.S. and Álvarez, R. and Vaz, B. and Faza, O.N. and De Lera, Á.R.},\ntitle={Simple diastereoselectivity of the BF3·OEt 2-catalyzed vinylogous Mukaiyama aldol reaction of 2-(trimethylsiloxy)furans with aldehydes},\njournal={Journal of Organic Chemistry},\nyear={2005},\nvolume={70},\nnumber={9},\npages={3654-3659},\ndoi={10.1021/jo0501339},\nabstract={(Chemical Equation Presented) A comprehensive scan of the transition state space for the reaction of 2-(trimethylsiloxy)furan and methacrolein (24 combinations) offered a satisfactory explanation of the high like diastereoselectivity obtained experimentally in the Mukaiyama vinylogous aldol reaction of these and related partners. It was determined that the syn-y-hydroxyalkylbutenolides are formed preferentially following a g + orientation of the two reactants with the aldehyde in the s-trans conformation. Diastereoselectivity is shown to be caused by a combination of subtle effects favoring the formation of the like product. © 2005 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n 2-Alkylidenesulfol-3-enes by (regio- and) stereoselective cheletropic addition of SO2 to (di)vinylallenes.\n \n \n \n\n\n \n Souto, J.; López, C.; Faza, O.; Alvarez, R.; and De Lera, A.\n\n\n \n\n\n\n Organic Letters, 7(8): 1565-1568. 2005.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Souto20051565,\nauthor={Souto, J.A. and López, C.S. and Faza, O.N. and Alvarez, R. and De Lera, A.R.},\ntitle={2-Alkylidenesulfol-3-enes by (regio- and) stereoselective cheletropic addition of SO2 to (di)vinylallenes},\njournal={Organic Letters},\nyear={2005},\nvolume={7},\nnumber={8},\npages={1565-1568},\ndoi={10.1021/ol050240p},\nabstract={(Chemical Equation Presented) The cheletropic addition of SO2 to divinylallenes is regioselective, taking place at the most substituted vinylallene and at the E unit if vinyl groups of opposite geometry are competing. Diastereofacial differentiation results from the approach of the reagent from the less-substituted direction of the allene and from the concomitant disrotatory movement of the termini of the vinylallene to afford the sterically more congested 2-alkylidenesulfol-3-ene isomer. DFT computations confirm the regio- and the stereoselectivity of these cheletropic additions. © 2005 American Chemical Society.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Pseudorotation barriers of biological oxyphosphoranes: A challenge for simulations of ribozyme catalysis.\n \n \n \n\n\n \n López, C.; Faza, O.; De Lera, A.; and York, D.\n\n\n \n\n\n\n Chemistry - A European Journal, 11(7): 2081-2093. 2005.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20052081,\nauthor={López, C.S. and Faza, O.N. and De Lera, A.R. and York, D.M.},\ntitle={Pseudorotation barriers of biological oxyphosphoranes: A challenge for simulations of ribozyme catalysis},\njournal={Chemistry - A European Journal},\nyear={2005},\nvolume={11},\nnumber={7},\npages={2081-2093},\ndoi={10.1002/chem.200400790},\nabstract={Pseudorotation reactions of biologically relevant oxyphosphoranes were studied by using density functional and continuum solvation methods. A series of 16 pseudorotation reactions involving acyclic and cyclic oxyphosphoranes in neutral and monoanionic (singly deprotonated) forms were studied, in addition to pseudorotation of PF5. The effect of solvent was treated by using three different solvation models for comparison. The barriers to pseudorotation ranged from 1.5 to 8.1 kcal mol-1 and were influenced systematically by charge state, apicophilicity of ligands, intramolecular hydrogen bonding, cyclic structure and solvation. Barriers to pseudorotation for monoanionic phosphoranes occur with the anionic oxo ligand as the pivotal atom, and are generally lower than for neutral phosphoranes. The OCH3 groups were observed to be more apicophilic than OH groups, and hence pseudorotations that involve axial OCH3/equatorial OH exchange had higher reaction and activation free energy values. Solvent generally lowered barriers relative to the gas-phase reactions. These results, together with isotope 18O exchange experiments, support the assertion that dianionic phosphoranes are not sufficiently long-lived to undergo pseudorotation. Comparison of the density functional results with those from several semiempirical quantum models highlight a challenge for new-generation hybrid quantum mechanical/molecular mechanical potentials for non-enzymatic and enzymatic phosphoryl transfer reactions: the reliable modeling of pseudorotation processes. © 2005 Wiley-VCH Verlag GmbH &amp; Co. KGaA.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Ellipticity: A convenient tool to characterize electrocyclic reactions.\n \n \n \n\n\n \n Silva López, C.; Nieto Faza, O.; Cossió, F.; York, D.; and De Lera, A.\n\n\n \n\n\n\n Chemistry - A European Journal, 11(6): 1734-1738. 2005.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{SilvaLopez20051734,\nauthor={Silva López, C. and Nieto Faza, O. and Cossió, F.P. and York, D.M. and De Lera, A.R.},\ntitle={Ellipticity: A convenient tool to characterize electrocyclic reactions},\njournal={Chemistry - A European Journal},\nyear={2005},\nvolume={11},\nnumber={6},\npages={1734-1738},\ndoi={10.1002/chem.200401026},\nabstract={The ellipticity of the electron density is proposed as a convenient tool to characterize electrocyclic reactions. The study of the electron density offers several advantages since it is an experimental observable. This simple topological index has proven powerful and robust for the characterization of a wide variety of electrocyclic and pseudoelectrocyclic processes. This property is sensitive to changes in the anisotropy of the electron density in the bond-forming region and provides an insightful description of the events occurring along the reaction coordinate. © 2005 Wiley-VCH Verlag GmbH Co. KGaA.},\n}\n\n

\n

\n\n\n\n\n\n

\n

\n \n 2004\n \n \n (7)\n \n \n

\n

\n \n \n

\n \n\n \n \n \n \n \n Solvolytic ring-opening reactions of cyclopropyl bromides. An assessment of the Woodward-Hoffmann-DePuy rule.\n \n \n \n\n\n \n Nieto Faza, O.; Silva López, C.; Álvarez, R.; and De Lera, Á.\n\n\n \n\n\n\n Journal of Organic Chemistry, 69(26): 9002-9010. 2004.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{NietoFaza20049002,\nauthor={Nieto Faza, O. and Silva López, C. and Álvarez, R. and De Lera, Á.R.},\ntitle={Solvolytic ring-opening reactions of cyclopropyl bromides. An assessment of the Woodward-Hoffmann-DePuy rule},\njournal={Journal of Organic Chemistry},\nyear={2004},\nvolume={69},\nnumber={26},\npages={9002-9010},\ndoi={10.1021/jo0487294},\nabstract={A theoretical study on the torquoselectivity of the electrocyclic ring opening of 2,3-disubstituted-mono and dibromo cyclopropanes was carried out at the B3LYP/6-311++G* level. As a result of charge donation from the dissociating C-C bond to the antibonding orbital of the breaking C-Br bond, only one of the two allowed disrotatory paths for the disrotatory ring opening, which takes place in concert with the C-Br bond cleavage, is energetically accessible, both in the gas phase and in solution. The general trends in torquoselectivity for these systems are not significantly affected by stereoelectronic effects of the substituents or the introduction of a second bromine in C1. For the Woodward-Hoffmann-DePuy-allowed processes, the remarkable lowering in energy when the OH or NH2 groups rotate inward can be attributed to the formation of an intramolecular X-H-Br hydrogen bond in the transition state. Aromaticity in reactants and transition states for the model systems is evaluated using a ring current model to shed light on the reaction mechanism.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Erratum: Pseudorotation of natural and chemically modified biological phosphoranes: Implications for RNA catalysis (ChemPhysChem (2004) 5 (1045-1049) DOI: 10.1002/cphc.200400091).\n \n \n \n\n\n \n López, C.; Faza, O.; Gregersen, B.; Lopez, X.; De Lera, A.; and York, D.\n\n\n \n\n\n\n ChemPhysChem, 5(9): 1266. 2004.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Lopez20041266,\nauthor={López, C.S. and Faza, O.N. and Gregersen, B.A. and Lopez, X. and De Lera, A.R. and York, D.M.},\ntitle={Erratum: Pseudorotation of natural and chemically modified biological phosphoranes: Implications for RNA catalysis (ChemPhysChem (2004) 5 (1045-1049) DOI: 10.1002/cphc.200400091)},\njournal={ChemPhysChem},\nyear={2004},\nvolume={5},\nnumber={9},\npages={1266},\ndoi={10.1002/cphc.200490049},\n}\n\n

\n

\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Theoretical study of the electrocyclic ring closure of hydroxypentadienyl cations.\n \n \n \n\n\n \n Nieto Faza, O.; Silva López, C.; Álvarez, R.; and De Lera, Á.\n\n\n \n\n\n\n Chemistry - A European Journal, 10(17): 4324-4333. 2004.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{NietoFaza20044324,\nauthor={Nieto Faza, O. and Silva López, C. and Álvarez, R. and De Lera, Á.R.},\ntitle={Theoretical study of the electrocyclic ring closure of hydroxypentadienyl cations},\njournal={Chemistry - A European Journal},\nyear={2004},\nvolume={10},\nnumber={17},\npages={4324-4333},\ndoi={10.1002/chem.200400037},\nabstract={At the 6-311G* level of theory, DFT methods predict that the rearrangement of 1,4-dihydroxy-5-methylpentadienyl cation 1 (R = Me) to protonated trans-3-hydroxy-2-methylcyclopent-4-en-1-one 2, an intermediate step in the Piancatelli reaction or rearrangement of furfuryl carbinols to trans-2-alkyl(aryl)-3-hydroxycyclopent-4-en-1-one, is a concerted electrocyclic process. Energetic, magnetic, and stereochemical criteria are consistent with a conrotatory electrocyclic ring closure of the most stable out,out-1 isomer to afford trans-2. Although the out,in-1 isomer is thermodynamically destabilized by 6.84 kcal mol-1, the activation energy for its cyclization is slightly lower (5.29 kcal mol-1 versus 5.95 kcal mol-1). The cyclization of the isomers of 1 with the C1-hydroxy group inwards showed considerably higher activation energies than their outwards counterparts. in,out-1, although close in energy to out,out-1 (difference of 1.57 kcal mol-1) required about 10 kcal mol-1 more to reach the corresponding transition structure. The value measured for the activation energy of in,in-1 (17.32 kcal mol-1) eliminates the alternative conrotatory electrocyclization of this isomer to provide trans-2. Geometric scrambling by isomerization of the terminal C1-C2 bond of 1 is also unlikely to compete with electrocyclization. The possibility to interpret the 1→2 reaction as a nonpericyclic cationic cyclization was also examined through NBO analysis, and the study of bond lengths and atomic charges. It was found that the 1→2 concerted rearrangement benefits from charge separation at the cyclization termini, an effect not observed in related concerted electrocyclic processes, such as the classical Nazarov reaction 3→4 or the cyclization of the isomeric 2-hydroxypentadienyl cation 5.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Pseudorotation of natural and chemically modified biological phosphoranes: Implications for RNA catalysis.\n \n \n \n\n\n \n Silva López, C.; Nieto Faza, O.; Gregersen, B.; Lopez, X.; De Lera, A.; and York, D.\n\n\n \n\n\n\n ChemPhysChem, 5(7): 1045-1049. 2004.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{SilvaLopez20041045,\nauthor={Silva López, C. and Nieto Faza, O. and Gregersen, B.A. and Lopez, X. and De Lera, A.R. and York, D.M.},\ntitle={Pseudorotation of natural and chemically modified biological phosphoranes: Implications for RNA catalysis},\njournal={ChemPhysChem},\nyear={2004},\nvolume={5},\nnumber={7},\npages={1045-1049},\ndoi={10.1002/cphc.200400091},\nabstract={Model intermediates: Catalytic mechanisms of RNA transphosphorylation are investigated by monitoring changes in the reaction rate that occur upon substitution of key phosphate oxygen atoms with sulfur atoms. The mechanisms and barriers to pseudorotation for a series of oxyphosphorane and thiophosphorane molecules are presented (see picture). Theoretical models provide detailed insight into biological phosphorous reactivity in RNA systems.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Theoretical study of the vinyl allene oxide to cyclopent-2-en-1-one rearrangement: Mechanism, torquoselectivity and solvent effects.\n \n \n \n\n\n \n Silva López, C.; Nieto Faza, O.; York, D.; and De Lera, A.\n\n\n \n\n\n\n Journal of Organic Chemistry, 69(11): 3635-3644. 2004.\n \n\n\n\n
\n\n\n\n \n\n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{SilvaLopez20043635,\nauthor={Silva López, C. and Nieto Faza, O. and York, D.M. and De Lera, A.R.},\ntitle={Theoretical study of the vinyl allene oxide to cyclopent-2-en-1-one rearrangement: Mechanism, torquoselectivity and solvent effects},\njournal={Journal of Organic Chemistry},\nyear={2004},\nvolume={69},\nnumber={11},\npages={3635-3644},\nabstract={Density-functional calculations in the gas phase and solvent (PCM) at the B3LYP/6-311++G(3df,-2p)//B3LYP/6-31++G(d,p) level were performed to study a series of six reactions that involve the rearrangement of vinyl allene oxides to cyclopent-2-en-1-ones along two distinct mechanistic pathways, namely concerted and stepwise. Calculations predict that stepwise pathways are highly competitive processes that occur via biradical/zwitterionic intermediates. Torquoselectivity is predicted to result from the concerted pathway leading to a stereodefined 4,5-disubstituted cyclopent-2-en-1-ones that should have memory of the starting terminal double-bond geometry and oxide configuration. The stepwise pathway cannot show torquoselectivity as cyclization of the planar oxidopentadienyl zwitterion can follow enantiomorphous conrotations. The concerted/stepwise mechanistic preference depends mainly on the olefin geometry and is further modulated by epoxide substitution. The influence of the solvent (PCM model for dichloromethane or water) is moderate, although the greater (de)stabilization of the polarized oxidopentadienyl zwitterions along the stepwise mechanism does alter the kinetic preferences exhibited by the systems in vacuo. Results with system 1e suggest that, if vinyl allene oxide II having a double bond with Z-geometry, an intermediate in the biogenesis of epi-jasmonic acid IV, is processed along an in stepwise mechanism following ring opening, the enzyme allene oxide cyclase must enforce enantiofacial torquoselectivity.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n The Woodward-Hoffmann-De Puy rule revisited.\n \n \n \n\n\n \n Faza, O.; López, C.; Álvarez, R.; and De Lera, Á.\n\n\n \n\n\n\n Organic Letters, 6(6): 905-908. 2004.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza2004905,\nauthor={Faza, O.N. and López, C.S. and Álvarez, R. and De Lera, Á.R.},\ntitle={The Woodward-Hoffmann-De Puy rule revisited},\njournal={Organic Letters},\nyear={2004},\nvolume={6},\nnumber={6},\npages={905-908},\ndoi={10.1021/ol036449p},\nabstract={(Equation presented) An estimate of the kinetic advantage, in the gas phase and in MeOH, of one of the two allowed disrotatory movements in the electrocyclic ring opening of cyclopropyl derivatives has been theoretically obtained at the B3LYP/6-311++G** level. Confirming the Woodward-Hoffmann-DePuy rule, the torquoselectivity of this process is attributed to charge donation from the dissociating C-C bond to the antibonding orbital of the breaking C-Br bond. Substituents do not modify the inherent torquoselectivity.},\n}\n\n

\n

\n\n\n\n\n\n

\n\n\n

\n \n\n \n \n \n \n \n Conrotatory ring-opening reactions of cyclopropyl anions in monocyclic and tricyclic systems.\n \n \n \n\n\n \n Faza, O.; López, C.; Álvarez, R.; and De Lera, Á.\n\n\n \n\n\n\n Organic Letters, 6(6): 901-904. 2004.\n \n\n\n\n
\n\n\n\n \n\n \n \n doi\n \n \n\n \n link\n \n \n\n bibtex\n \n\n \n \n \n abstract \n \n\n \n\n \n \n \n \n \n \n \n\n \n \n \n\n\n\n

\n

@ARTICLE{Faza2004901,\nauthor={Faza, O.N. and López, C.S. and Álvarez, R. and De Lera, Á.R.},\ntitle={Conrotatory ring-opening reactions of cyclopropyl anions in monocyclic and tricyclic systems},\njournal={Organic Letters},\nyear={2004},\nvolume={6},\nnumber={6},\npages={901-904},\ndoi={10.1021/ol036448x},\nabstract={(Equation presented) Only conrotatory transition structures were located by B3LYP6-311++G(3df, 2p) computations for the electrocyclic ring opening of cyclopropyl anions having different substituents (H, Me, CN). The transition structure for the similarly substituted cyclopropyl anion fused to a bicyclic system exhibits the same features, in apparent contradiction with the observed product. A reaction path where the direction of twist changes after the transition state provides an explanation alternative to those proposed in recent reports.},\n}\n

\n

\n\n\n\n\n\n

\n