Bicyclic Guanidine-Catalyzed Asymmetric Cycloaddition Reaction of Anthrones—Bifunctional Binding Modes and Origin of Stereoselectivity

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Bicyclic Guanidine-Catalyzed Asymmetric Cycloaddition Reaction of Anthrones—Bifunctional Binding Modes and Origin of Stereoselectivity
Title:
Bicyclic Guanidine-Catalyzed Asymmetric Cycloaddition Reaction of Anthrones—Bifunctional Binding Modes and Origin of Stereoselectivity
Journal Title:
Journal of Organic Chemistry
Keywords:
Publication Date:
11 November 2020
Citation:
J. Org. Chem. 2020, 85, 23, 15139–15153
Abstract:
We report a computational analysis of the [5,5] bicyclic guanidine-catalyzed asymmetric cycloaddition reaction of anthrones. Based on extensive conformational search of key intermediates and transition states on the potential energy surface and density functional theory calculations, we studied five plausible binding modes between the guanidine catalyst and substrates for this reaction. Our results indicate that the most favorable pathway is a stepwise conjugate addition-Aldol sequence via the dual hydrogen-bond binding mode. The predicted level of enantioselectivity is in good agreement with experimental values. Trends in variation of substrates and catalysts have also been reproduced by our calculations. Decomposition analysis revealed the significance of aromatic interactions in stabilizing the key enantioselectivity-determining transition state structures.
License type:
Publisher Copyright
Funding Info:
This research / project is supported by the Institute of Chemical and Engineering Sciences - Project
Grant Reference no. : SC22/17-1A02G4

This research / project is supported by the National University of Singapore - Grant
Grant Reference no. : R-143-000-481-112
Description:
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.0c02008.
ISSN:
0022-3263
1520-6904
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