Asymmetric one-carbon ring expansion of diverse N-heterocycles via copper-catalyzed diyne cyclization

作者：Fu‐Shuai Li, Xiuyuan Zou, Tian-Qi Hu, Qing Sun, Zhou Xu, Bo Zhou, Long‐Wu Ye · 发表于：Science Advances · 年份：2024 · DOI：10.1126/sciadv.adq7767 · 被引用次数：26 · 研究领域：Catalytic Alkyne Reactions、Catalytic C–H Functionalization Methods、Catalytic Cross-Coupling Reactions

One-carbon ring expansion reaction of N-heterocycles has gained particular attention in the past decade because this method allows for the conversion of readily available N-heterocycles into potentially useful complex ring-expanded N-heterocycles, which are inaccessible by traditional methods. However, the catalytic asymmetric variant of this reaction has been rarely reported to date. Herein, we disclose an enantioselective one-carbon ring expansion reaction through chiral copper-catalyzed diyne cyclization, leading to the practical, atom-economic and divergent assembly of an array of valuable chiral N-heterocycles bearing a quaternary stereocenter in generally good to excellent yields with excellent enantioselectivities (up to >99% ee). This protocol represents the first example of asymmetric one-carbon ring expansion reaction of N-heterocycles based on alkynes.