The influence of organosuperbases on the structure and activity of dialkylgallium alkoxides in the polymerization of rac‐lactide: the road to stereo diblock PLA copolymers. Horeglad, P., Litwińska, A., Żukowska, G. Z., Kubicki, D. J., Szczepaniak, G., Dranka, M., & Zachara, J. Applied Organometallic Chemistry, 27(6):328–336, May, 2013. MAG ID: 2555462681doi abstract bibtex Stereoselective polymerization of rac-lactide is one of the most important issues as the properties of polylactide (PLA) depend strongly on its tacticity. There is, however, a paucity of catalysts that allow for easy switching between heteroselectivity and isoselectivity, which limits the synthesis of stereo copolymers of PLA and modification of polylactide properties. Dialkylgallium alkoxides activated by organosuperbases have been used as catalysts in the ring-opening polymerization of racemic lactide (rac-LA). The reaction of (S,S)-[Me2Ga(μ-OCH(Me)CO2Me)]2 (1) with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) resulted in the formation of isoselective gallium species, highly active in the polymerization of rac-LA. DOSY (diffusion-ordered spectroscopy) NMR was indicative for the presence of dimeric gallium species. However, the structure of model monomeric gallium alkoxide Me2Ga(ON) (where ON is monoanionic bidentate ligand possessing organosuperbase functionality) shows that the presence of an organosuperbase may substantially weaken Ga−Oalkoxide−Ga bridges. The facile switch of stereoselectivity upon addition of organosuperbase to nonselective/heteroselective 1 allowed for the first time the synthesis of diblock polylactide comprised of isotactically and heterotactically enriched blocks. Copyright © 2013 John Wiley & Sons, Ltd.
@article{horeglad_influence_2013,
title = {The influence of organosuperbases on the structure and activity of dialkylgallium alkoxides in the polymerization of rac‐lactide: the road to stereo diblock {PLA} copolymers},
volume = {27},
doi = {10.1002/aoc.2978},
abstract = {Stereoselective polymerization of rac-lactide is one of the most important issues as the properties of polylactide (PLA) depend strongly on its tacticity. There is, however, a paucity of catalysts that allow for easy switching between heteroselectivity and isoselectivity, which limits the synthesis of stereo copolymers of PLA and modification of polylactide properties. Dialkylgallium alkoxides activated by organosuperbases have been used as catalysts in the ring-opening polymerization of racemic lactide (rac-LA). The reaction of (S,S)-[Me2Ga(μ-OCH(Me)CO2Me)]2 (1) with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) resulted in the formation of isoselective gallium species, highly active in the polymerization of rac-LA. DOSY (diffusion-ordered spectroscopy) NMR was indicative for the presence of dimeric gallium species. However, the structure of model monomeric gallium alkoxide Me2Ga(ON) (where ON is monoanionic bidentate ligand possessing organosuperbase functionality) shows that the presence of an organosuperbase may substantially weaken Ga−Oalkoxide−Ga bridges. The facile switch of stereoselectivity upon addition of organosuperbase to nonselective/heteroselective 1 allowed for the first time the synthesis of diblock polylactide comprised of isotactically and heterotactically enriched blocks. Copyright © 2013 John Wiley \& Sons, Ltd.},
number = {6},
journal = {Applied Organometallic Chemistry},
author = {Horeglad, Paweł and Litwińska, Anna and Żukowska, Grażyna Z. and Kubicki, Dominik J. and Szczepaniak, Grzegorz and Dranka, Maciej and Zachara, Janusz},
month = may,
year = {2013},
doi = {10.1002/aoc.2978},
note = {MAG ID: 2555462681},
keywords = {\#nosource},
pages = {328--336},
}
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There is, however, a paucity of catalysts that allow for easy switching between heteroselectivity and isoselectivity, which limits the synthesis of stereo copolymers of PLA and modification of polylactide properties. Dialkylgallium alkoxides activated by organosuperbases have been used as catalysts in the ring-opening polymerization of racemic lactide (rac-LA). The reaction of (S,S)-[Me2Ga(μ-OCH(Me)CO2Me)]2 (1) with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) resulted in the formation of isoselective gallium species, highly active in the polymerization of rac-LA. DOSY (diffusion-ordered spectroscopy) NMR was indicative for the presence of dimeric gallium species. However, the structure of model monomeric gallium alkoxide Me2Ga(ON) (where ON is monoanionic bidentate ligand possessing organosuperbase functionality) shows that the presence of an organosuperbase may substantially weaken Ga−Oalkoxide−Ga bridges. The facile switch of stereoselectivity upon addition of organosuperbase to nonselective/heteroselective 1 allowed for the first time the synthesis of diblock polylactide comprised of isotactically and heterotactically enriched blocks. Copyright © 2013 John Wiley & Sons, Ltd.","number":"6","journal":"Applied Organometallic Chemistry","author":[{"propositions":[],"lastnames":["Horeglad"],"firstnames":["Paweł"],"suffixes":[]},{"propositions":[],"lastnames":["Litwińska"],"firstnames":["Anna"],"suffixes":[]},{"propositions":[],"lastnames":["Żukowska"],"firstnames":["Grażyna","Z."],"suffixes":[]},{"propositions":[],"lastnames":["Kubicki"],"firstnames":["Dominik","J."],"suffixes":[]},{"propositions":[],"lastnames":["Szczepaniak"],"firstnames":["Grzegorz"],"suffixes":[]},{"propositions":[],"lastnames":["Dranka"],"firstnames":["Maciej"],"suffixes":[]},{"propositions":[],"lastnames":["Zachara"],"firstnames":["Janusz"],"suffixes":[]}],"month":"May","year":"2013","note":"MAG ID: 2555462681","keywords":"#nosource","pages":"328–336","bibtex":"@article{horeglad_influence_2013,\n\ttitle = {The influence of organosuperbases on the structure and activity of dialkylgallium alkoxides in the polymerization of rac‐lactide: the road to stereo diblock {PLA} copolymers},\n\tvolume = {27},\n\tdoi = {10.1002/aoc.2978},\n\tabstract = {Stereoselective polymerization of rac-lactide is one of the most important issues as the properties of polylactide (PLA) depend strongly on its tacticity. 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