Dynamic Kinetic Asymmetric Hydroacylation: Racemization by Soft Enolization

Mengfei Xu; Stephanie A. Corio; Josephine M. Warnica; Erin L. Kuker; Alexander Lu; Jennifer S. Hirschi; Vy M. Dong

doi:10.1021/jacs.5c01753

Dynamic Kinetic Asymmetric Hydroacylation: Racemization by Soft Enolization

Mengfei Xu
, Stephanie A. Corio
, Josephine M. Warnica
, Erin L. Kuker
, Alexander Lu
, Jennifer S. Hirschi
, Vy M. Dong

Chemistry

Binghamton University

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

We report a dynamic kinetic asymmetric transformation (DyKAT) of racemic aldehydes by Rh-catalyzed hydroacylation of acrylamides. This intermolecular hydroacylation generates 1,4-ketoamides with high enantio- and diastereoselectivity. DFT and experimental studies provide mechanistic insights and reveal an unexpected Rh-catalyzed pathway for aldehyde racemization. Our study represents a pioneering kinetic resolution by intermolecular hydroacylation and contributes to the growing field of stereoconvergent catalysis featuring C–C bond construction.

Original language	English
Pages (from-to)	16270-16281
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	147
Issue number	19
DOIs	https://doi.org/10.1021/jacs.5c01753
State	Published - May 14 2025

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title = "Dynamic Kinetic Asymmetric Hydroacylation: Racemization by Soft Enolization",

abstract = "We report a dynamic kinetic asymmetric transformation (DyKAT) of racemic aldehydes by Rh-catalyzed hydroacylation of acrylamides. This intermolecular hydroacylation generates 1,4-ketoamides with high enantio- and diastereoselectivity. DFT and experimental studies provide mechanistic insights and reveal an unexpected Rh-catalyzed pathway for aldehyde racemization. Our study represents a pioneering kinetic resolution by intermolecular hydroacylation and contributes to the growing field of stereoconvergent catalysis featuring C–C bond construction.",

author = "Mengfei Xu and Corio, \{Stephanie A.\} and Warnica, \{Josephine M.\} and Kuker, \{Erin L.\} and Alexander Lu and Hirschi, \{Jennifer S.\} and Dong, \{Vy M.\}",

note = "Publisher Copyright: {\textcopyright} 2025 The Authors. Published by American Chemical Society",

year = "2025",

month = may,

day = "14",

doi = "10.1021/jacs.5c01753",

language = "English",

volume = "147",

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journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - Dynamic Kinetic Asymmetric Hydroacylation

T2 - Racemization by Soft Enolization

AU - Xu, Mengfei

AU - Corio, Stephanie A.

AU - Warnica, Josephine M.

AU - Kuker, Erin L.

AU - Lu, Alexander

AU - Hirschi, Jennifer S.

AU - Dong, Vy M.

PY - 2025/5/14

Y1 - 2025/5/14

N2 - We report a dynamic kinetic asymmetric transformation (DyKAT) of racemic aldehydes by Rh-catalyzed hydroacylation of acrylamides. This intermolecular hydroacylation generates 1,4-ketoamides with high enantio- and diastereoselectivity. DFT and experimental studies provide mechanistic insights and reveal an unexpected Rh-catalyzed pathway for aldehyde racemization. Our study represents a pioneering kinetic resolution by intermolecular hydroacylation and contributes to the growing field of stereoconvergent catalysis featuring C–C bond construction.

AB - We report a dynamic kinetic asymmetric transformation (DyKAT) of racemic aldehydes by Rh-catalyzed hydroacylation of acrylamides. This intermolecular hydroacylation generates 1,4-ketoamides with high enantio- and diastereoselectivity. DFT and experimental studies provide mechanistic insights and reveal an unexpected Rh-catalyzed pathway for aldehyde racemization. Our study represents a pioneering kinetic resolution by intermolecular hydroacylation and contributes to the growing field of stereoconvergent catalysis featuring C–C bond construction.

UR - https://www.scopus.com/pages/publications/105004047969

U2 - 10.1021/jacs.5c01753

DO - 10.1021/jacs.5c01753

M3 - Article

C2 - 40298317

SN - 0002-7863

VL - 147

SP - 16270

EP - 16281

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 19

ER -

Dynamic Kinetic Asymmetric Hydroacylation: Racemization by Soft Enolization

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