Nickel‐Catalyzed Atroposelective Carbo‐Carboxylation of Alkynes with CO 2 : En Route to Axially Chiral Carboxylic Acids

作者：Chao Li, Xiao‐Wang Chen, Li‐Li Liao, Yong‐Yuan Gui, Yong‐Yuan Gui, Jing‐Wei Yang, Shuo Zhang, Jun‐Ping Yue, Xiangge Zhou, Xiangge Zhou, Jian‐Heng Ye, Yu Lan, Da‐Gang Yu · 发表于：Angewandte Chemie International Edition · 年份：2024 · DOI：10.1002/anie.202413305 · 被引用次数：24 · 研究领域：Carbon dioxide utilization in catalysis、Catalytic C–H Functionalization Methods、Asymmetric Synthesis and Catalysis

Abstract Precise synthesis of carboxylic acids via catalytic carboxylation with CO 2 is highly appealing. Although considerable advancements have been achieved in difunctionalizing carboxylation of unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly in addressing axially chiral alkenes. Herein, we report the first catalytic atroposelective carboxylation of alkynes with CO 2 . A variety of valuable axially chiral carboxylic acids are obtained with good yields and high chemo‐, regio‐, Z/E and enantio‐selectivities. Notably, an unexpected anti ‐selective carbo‐carboxylation is observed in the sp 2 ‐hybrid carbo‐electrophile‐initiated reductive carboxylation of alkynes. Mechanistic studies including DFT calculation elucidate the origin of chiral induction and anti ‐selectivity in vinyl‐carboxylation of alkynes.