Novel chiral norbornadiene–quadricyclane systems: substituent effect on chiroptical properties and stereochemical consequence of photochemical interconversion. Nishino, H., Nakamura, A., Terada, M., Kosaka, A., Fukui, M., Aoki, N., & Inoue, Y. Journal of Photochemistry and Photobiology A: Chemistry, 147(1):1–14, 2002. ![Novel chiral norbornadiene–quadricyclane systems: substituent effect on chiroptical properties and stereochemical consequence of photochemical interconversion [link]](https://bibbase.org/img/filetypes/link.svg "link")
Paper doi abstract bibtex For efficient absolute asymmetric synthesis (AAS) by circularly polarized light (CPL), a series of 3-substituted 2-methoxycarbonylnorbornadiene (N) and -quadricyclane (Q) derivatives (R=H, Me, Ph, 4-biphenylyl, 1- and 2-naphthyl) were prepared and optically resolved, and the chiroptical properties of the enantiomeric pairs were determined in hexane and acetonitrile. All of the N and Q derivatives gave moderate to large circular dichroism intensities (Δε) and specific rotations ([α]D). In particular, aromatic Ns (R=4-biphenylyl and 2-naphthyl) gave high [α]D values of 216° and 206°, while non-aromatic Qs (R=H and Me) afforded high [α]D’s of 322° and 271°. Depending on the nature of the substituent introduced at the 3-position, the maximum anisotropy factor (g=Δε/ε) varied over a wide range from 0.0141 (R=H) to 0.0022 (R=1-naphthyl) in the N series and from 0.0091 (R=Me) to 0.0012 for (R=2-naphthyl) in the Q series. Thus, non-aromatic N/Q pair is absolutely advantageous for the CPL-induced AAS reactions. The relatively high gmax values observed for non-aromatic Ns and Qs may be rationalized by the contribution of the n, π∗ transition of the ester chromophore to the N and Q chromophores. Stereochemical consequence of the photochemical interconversion of the chiral N and Q was also revealed; all of the (−)-Ns examined photoisomerized to the corresponding (+)-Qs without any side reactions.
@article{nishino_novel_2002,
title = {Novel chiral norbornadiene–quadricyclane systems: substituent effect on chiroptical properties and stereochemical consequence of photochemical interconversion},
volume = {147},
url = {http://dx.doi.org/10.1016/S1010-6030(01)00633-5},
doi = {10.1016/S1010-6030(01)00633-5},
abstract = {For efficient absolute asymmetric synthesis (AAS) by circularly polarized light (CPL), a series of 3-substituted 2-methoxycarbonylnorbornadiene (N) and -quadricyclane (Q) derivatives (R=H, Me, Ph, 4-biphenylyl, 1- and 2-naphthyl) were prepared and optically resolved, and the chiroptical properties of the enantiomeric pairs were determined in hexane and acetonitrile. All of the N and Q derivatives gave moderate to large circular dichroism intensities (Δε) and specific rotations ([α]D). In particular, aromatic Ns (R=4-biphenylyl and 2-naphthyl) gave high [α]D values of 216° and 206°, while non-aromatic Qs (R=H and Me) afforded high [α]D’s of 322° and 271°. Depending on the nature of the substituent introduced at the 3-position, the maximum anisotropy factor (g=Δε/ε) varied over a wide range from 0.0141 (R=H) to 0.0022 (R=1-naphthyl) in the N series and from 0.0091 (R=Me) to 0.0012 for (R=2-naphthyl) in the Q series. Thus, non-aromatic N/Q pair is absolutely advantageous for the CPL-induced AAS reactions. The relatively high gmax values observed for non-aromatic Ns and Qs may be rationalized by the contribution of the n, π∗ transition of the ester chromophore to the N and Q chromophores. Stereochemical consequence of the photochemical interconversion of the chiral N and Q was also revealed; all of the (−)-Ns examined photoisomerized to the corresponding (+)-Qs without any side reactions.},
number = {1},
journal = {Journal of Photochemistry and Photobiology A: Chemistry},
author = {Nishino, Hideo and Nakamura, Asao and Terada, Mariko and Kosaka, Atsuko and Fukui, Mieko and Aoki, Noriko and Inoue, Yoshihisa},
year = {2002},
keywords = {absolute asymmetric synthesis, anisotropy factor, chiroptical property, circular dichroism, norbornadiene, quadricyclane, specific rotation},
pages = {1--14},
}
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All of the N and Q derivatives gave moderate to large circular dichroism intensities (Δε) and specific rotations ([α]D). In particular, aromatic Ns (R=4-biphenylyl and 2-naphthyl) gave high [α]D values of 216° and 206°, while non-aromatic Qs (R=H and Me) afforded high [α]D’s of 322° and 271°. Depending on the nature of the substituent introduced at the 3-position, the maximum anisotropy factor (g=Δε/ε) varied over a wide range from 0.0141 (R=H) to 0.0022 (R=1-naphthyl) in the N series and from 0.0091 (R=Me) to 0.0012 for (R=2-naphthyl) in the Q series. Thus, non-aromatic N/Q pair is absolutely advantageous for the CPL-induced AAS reactions. The relatively high gmax values observed for non-aromatic Ns and Qs may be rationalized by the contribution of the n, π∗ transition of the ester chromophore to the N and Q chromophores. 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