Hydrogen Bond Enhanced Enantioselectivity in the Nickel-Catalyzed Transfer Hydrogenation of α-Substituted Acrylic Acid with Formic Acid

作者：Yaxin Sun, Chao Wang, Peng Yang, Jieyu Yue, Chang Xu, Jianrong Steve Zhou, Bo Tang · 发表于：ACS Catalysis · 年份：2023 · DOI：10.1021/acscatal.3c04187 · 被引用次数：25 · 研究领域：Asymmetric Hydrogenation and Catalysis、Carbon dioxide utilization in catalysis、Chemical Synthesis and Analysis

A chiral nickel complex that catalyzed asymmetric transfer hydrogenation of α-substituted acrylic acids under mild conditions and avoided the use of high-pressure hydrogen gas was developed. The products included chiral β-amino acids and α-methyl carboxylic acids such as three nonsteroidal anti-inflammatory profens. Deuterium-labeling experiments and DFT studies pointed to an unconventional protonation of a metalacyclopropane complex formed by α-phenylacrylic acid which was hydrogen bonded with formic acid. An alternative conventional pathway of nickel hydride insertion cannot explain selective deuteration at β-position of α-phenylacrylic acid when HCO 2 D was used.