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Enantiodivergence April 14th.pdf (2.25 MB)

Origin of Enantioselectivity Reversal in Lewis Acid-Catalysed Michael Additions Relying on the Same Chiral Source

preprint
revised on 15.04.2021, 02:22 and posted on 15.04.2021, 10:33 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 as reagent. 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 the potential significance, general catalytic methods to effectively reverse enantioselectivity by changing an achiral reaction parameter remain underdeveloped. Herein we report our studies focused on elucidating the origin of metal-controlled enantioselectivity reversal in Lewis acid-catalysed Michael additions. Rigorous experimental and computational investigations reveal that specific interactions between the substrate and ligand depending on the choice of metal catalyst are a key factor responsible for the observed enantiodivergence. This holds potential to further our understanding of and facilitate the design of future enantiodivergent transformations.

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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