Dynamic Kinetic Asymmetric Hydroacylation: Racemization by Soft Enolization

作者：Mengfei Xu, Stephanie A. Corio, Josephine M. Warnica, Erin L. Kuker, Alexander Lu, Jennifer S. Hirschi, Vy M. Dong · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c01753 · 被引用次数：6 · 研究领域：Asymmetric Hydrogenation and Catalysis、Catalytic C–H Functionalization Methods、Asymmetric Synthesis and Catalysis

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.