Copper‐Catalyzed Asymmetric Cyanation of Propargylic Radicals Derived From Silyl‐Substituted Allenes and Alkynes

作者：Zhongming Cheng, Guoyu Zhang, Yunshun Deng, Yiping Zhang, Li Xiang, Pinhong Chen, Guosheng Liu · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202505939 · 被引用次数：11 · 研究领域：Catalytic C–H Functionalization Methods、Radical Photochemical Reactions、Catalytic Cross-Coupling Reactions

Abstract Here, we report an efficient method to synthesize enantiomerically enriched propargyl nitriles via copper‐catalyzed asymmetric cyanation of propargylic radicals, which are generated from silyl‐substituted allenes or alkynes. These reactions proceeded through a highly site‐selective hydrogen atom abstraction (HAA) with Cu(II)‐bound nitrogen‐centered radicals (NCRs). Notably, silyl‐substituted allenes demonstrate exceptional allenic sp 2 C─H bond activation selectivity, outcompeting alternative reactive sp 3 C─H bonds (benzylic, allylic, and heteroatom‐adjacent) in HAA processes. This chemo‐selectivity profile enables precise enantiocontrol and site‐specific functionalization of complex molecular architectures.