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Enantiodivergence June 16th.pdf (1.38 MB)
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Thermodynamic vs. Kinetic Control Enables Lewis Acid-Induced Enantioselectivity Reversal Relying on the Same Chiral Source

preprint
revised on 17.06.2020 and posted on 18.06.2020 by Paul S. Riehl, Alistair D. Richardson, Tatsuhiro Sakamoto, Jolene P. Reid, Corinna Schindler
Enantiodivergence is an important concept in asymmetric catalysis that enables access to both enantiomers of a product relying on the same chiral source. This strategy is particularly appealing as an alternate approach when only one enantiomer of the required chiral ligand is readily accessible but both enantiomers of the product are desired. Despite their potential significance, general catalytic methods to induce reversal in enantioselectivity remain underdeveloped. Herein we report our studies focused on elucidating the origin of enantioselectivity reversal in Lewis acid-catalyzed Michael additions relying on the same enantiomer of ligand as the chiral source. Our results provide a detailed mechanistic understanding of this transformation based on experimental and computational investigations which reveal the important interplay between kinetics and thermodynamics responsible for the observed enantiodivergence.

History

Email Address of Submitting Author

corinnas@umich.edu

Institution

University of Michigan

Country

United States

ORCID For Submitting Author

0000-0003-4968-8013

Declaration of Conflict of Interest

No conflict of interest.

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