Regiodivergent Hydroamidation of Alkenes via Cobalt-Hydride Catalysis

作者：Bingxue Liu, Qianqian Lü, Xiao Hu, Dandan Li, Zheyuan Xu, Xi Lu, Yao Fu, Qiang Liu · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c03484 · 被引用次数：16 · 研究领域：Asymmetric Hydrogenation and Catalysis、Catalytic C–H Functionalization Methods、Synthesis and Catalytic Reactions

Regiodivergent hydroamin(d)ation of alkenes presents a valuable strategy for the synthesis of diverse amines or amides from a common set of starting materials, yet achieving controlled regioselectivity remains a significant challenge. In this work, we present a cobalt-catalyzed regiodivergent hydroamidation of alkenes, enabling enantioselective ipso - and migratory hydroamidation of heterocyclic alkenes. The ability to finely tune various reaction parameters allows for a seamless switch in regioselectivity. Notably, ipso - and migratory selectivity are governed by the choice of cobalt catalyst anions. Mechanistic studies reveal a neutral Co–H species mediating ipso -hydroamidation and a cationic Co–H intermediate promoting migratory hydroamidation. This protocol exhibits a broad substrate scope, high functional group tolerance, and provides an efficient pathway for synthetizing structurally diverse amides.