The Interplay Between Conformation and Absolute Configuration in Chiral Electron Dynamics of Small Diols

Daly, Steven; Daly, Stephen; Tia, Maurice; Garcia, Gustavo A.; Nahon, Laurent; Powis, Ivan

Abstract

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim A competition between chiral characteristics alternatively attributable to either conformation or to absolute configuration is identified. Circular dichroism associated with photoexcitation of the outer orbital of configurational enantiomers of 1,3- and 2,3-butanediols has been examined with a focus on the large changes in electron chiral asymmetry produced by different molecular conformations. Experimental gas-phase measurements offer support for the theoretical modeling of this chiroptical effect. A surprising prediction is that a conformationally produced pseudo-enantiomerism in 1,3-butanediol generates a chiral response in the frontier electron dynamics that outweighs the influence of the permanent configurational handedness established at the asymmetrically substituted carbon. Induced conformation, and specifically induced conformational chirality, may thus be a dominating factor in chiral molecular recognition in such systems.

Citation

Daly, S., Daly, S., Tia, M., Garcia, G. A., Nahon, L., & Powis, I. (2016). The Interplay Between Conformation and Absolute Configuration in Chiral Electron Dynamics of Small Diols. Angewandte Chemie International Edition, 55(37), 11054-11058. https://doi.org/10.1002/anie.201603771

• Journal Article Type: Article
• Acceptance Date: Jun 16, 2016
• Online Publication Date: Jul 22, 2016
• Publication Date: Sep 5, 2016
• Deposit Date: Aug 8, 2016
• Publicly Available Date: Aug 8, 2016
• Journal: Angewandte Chemie International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 55
• Issue: 37
• Pages: 11054-11058
• DOI: https://doi.org/10.1002/anie.201603771
• Public URL: https://nottingham-repository.worktribe.com/output/799791
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/anie.201603771/abstract
• Additional Information: This is the peer reviewed version of the following article: Daly, S., Tia, M., Garcia, G. A., Nahon, L. and Powis, I. (2016), The Interplay Between Conformation and Absolute Configuration in Chiral Electron Dynamics of Small Diols. Angew. Chem. Int. Ed.. doi:10.1002/anie.201603771, which has been published in final form athttp://onlinelibrary.wiley.com/doi/10.1002/anie.201603771/abstract. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
• Contract Date: Aug 8, 2016