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动态动力学不对称氢酰化反应：通过温和烯醇化实现外消旋化

Dynamic Kinetic Asymmetric Hydroacylation: Racemization by Soft Enolization.

作者信息

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

机构信息

Department of Chemistry, University of California, Irvine, California 92697, United States.

Department of Chemistry, Binghamton University, Binghamton, New York 13902, United States.

出版信息

J Am Chem Soc. 2025 May 14;147(19):16270-16281. doi: 10.1021/jacs.5c01753. Epub 2025 Apr 29.

DOI:10.1021/jacs.5c01753
PMID:40298317
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12082635/
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.

摘要

我们报道了通过铑催化丙烯酰胺的氢酰化反应实现外消旋醛的动态动力学不对称转化（DyKAT）。这种分子间氢酰化反应能以高对映选择性和非对映选择性生成1,4 - 酮酰胺。密度泛函理论（DFT）和实验研究提供了机理见解，并揭示了一种意外的铑催化醛消旋化途径。我们的研究代表了通过分子间氢酰化反应进行的开创性动力学拆分，并为以C - C键构建为特征的立体汇聚催化这一不断发展的领域做出了贡献。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/f3b0f31648b4/ja5c01753_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/4c9d4d97e805/ja5c01753_0001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/d3761f1e28f0/ja5c01753_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/17119fe641f7/ja5c01753_0008.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/0aebab0718e9/ja5c01753_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/f3b0f31648b4/ja5c01753_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/4c9d4d97e805/ja5c01753_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/ac1527827920/ja5c01753_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/013c17356df0/ja5c01753_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/d3761f1e28f0/ja5c01753_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/17119fe641f7/ja5c01753_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/2665a63e0246/ja5c01753_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/95bc0ff701ff/ja5c01753_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/0aebab0718e9/ja5c01753_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/682e/12082635/f3b0f31648b4/ja5c01753_0006.jpg

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Dynamic Kinetic Resolution of β-Cyano α-Ketoesters via Asymmetric Transfer Hydrogenation.通过不对称转移氢化实现β-氰基α-酮酯的动态动力学拆分
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A Merger of Relay Catalysis with Dynamic Kinetic Resolution Enables Enantioselective β-C(sp)-H Arylation of Alcohols.
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A directed enolization strategy enables by-product-free construction of contiguous stereocentres en route to complex amino acids.导向的烯醇化策略可实现无副产物构建连续立体中心，从而合成复杂氨基酸。
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