Xu Mengfei, Corio Stephanie A, Warnica Josephine M, Kuker Erin L, Lu Alexander, Hirschi Jennifer S, Dong Vy M
Department of Chemistry, University of California, Irvine, California 92697, United States.
Department of Chemistry, Binghamton University, Binghamton, New York 13902, United States.
J Am Chem Soc. 2025 May 14;147(19):16270-16281. doi: 10.1021/jacs.5c01753. Epub 2025 Apr 29.
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.
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。
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