Structural Dynamics and Stereoselectivity of Chiral Benzylideneamine N,C‐Chelate Borane Photo–Thermal Isomerization
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Authors
Novoseltseva, Polina
Li, Haijun
Wang, Xiang
Sauriol, Francoise
Wang, Suning
Date
2020-01-03
Type
journal article
Language
en
Keyword
Boranes , Diastereoselectivity , Mechanisms , Photoisomerization , Structure Elucidation
Alternative Title
Abstract
New chiral N,C-chelate organoboron compounds based on benzylideneamines (bza) with the general formula of B(bza-R)Mes2 (R=H or Me; Mes=mesityl) are reported. A chiral substituent group R- or S-CH(CH3)Ph (Ph=phenyl) was introduced to the imine center, which imposed a previously unobserved pseudo- or axial-chirality on the BMes2, creating distinct diastereomers. NMR spectroscopic studies established that the diastereomers undergo slow exchange in solution at ambient temperature. The chiral N,C-chelate B(bza-R)Mes2 molecules undergo photoisomerization in the same manner as their non-chiral analogues, generating chiral BN-cyclooctatriene (BN-COT) derivatives. Most significantly, by tracking the photoisomerization with circular dichroism (CD) and 1H?NMR spectra along with time-dependent density functional theory (TD-DFT) computational studies, the photoisomerization was established to proceed in a highly stereoselective manner, that is, one diastereomer converts exclusively to the corresponding diastereomer product in the photoreaction.
Description
This is the peer reviewed version of the following article: Structural Dynamics and Stereoselectivity of Chiral Benzylideneamine N,C‐Chelate Borane Photo–Thermal Isomerization Polina Novoseltseva Dr. Haijun Li Dr. Xiang Wang Dr. Francoise Sauriol Prof. Dr. Suning Wang Chemistry-A European Journal 2020 26 (10), 2276-2284 DOI:10.1002/chem.201905312, which has been published in final form at https://doi.org/10.1002/chem.201905312. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Citation
Structural Dynamics and Stereoselectivity of Chiral Benzylideneamine N,C‐Chelate Borane Photo–Thermal Isomerization Polina Novoseltseva Dr. Haijun Li Dr. Xiang Wang Dr. Francoise Sauriol Prof. Dr. Suning Wang Chemistry-A European Journal 2020 26 (10), 2276-2284 DOI:10.1002/chem.201905312
Publisher
Wiley