Copper‐Catalyzed Asymmetric Cyanation of Propargylic Radicals Derived From Silyl‐Substituted Allenes and Alkynes
Abstract
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.
Article Details
Authors (7)
Zhongming Cheng
State Key Laboratory of Organometallic Chemistry, and Shanghai Hongkong Joint Laboratory in Chemical Synthesis
Guoyu Zhang
New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, and Shanghai Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences, Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
Yunshun Deng
New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
Yiping Zhang
Xiang Li
Pinhong Chen
State Key Laboratory of Organometallic Chemistry, and Shanghai Hongkong Joint Laboratory in Chemical Synthesis
Guosheng Liu