Enantioselective Remote Alkylation Enabled by Metallaphotoredox Catalysis via Selective C–C Bond Cleavage
Ao Yu, Ning Wang, Siyuan Tang, Zhan Jie Wang, Liang‐Hua Zou, Huan‐Ming Huang
Abstract
Despite recent advances in enantioselective radical coupling with strained cyclic rings, asymmetric radical reactions triggered by unstrained cyclic motifs remain rare. Herein, we report a mild and general strategy for activating a diverse set of readily available unstrained cyclic alcohols for the remote and site-specific allylic alkylation of ketones through a combination of photoredox-mediated proton-coupled electron transfer and chiral chromium catalysis. This newly developed dual catalytic system exhibits extensive applicability, operates under mild conditions, offers straightforward operation, and demonstrates tolerance to diverse functional groups. The open-shell strategy has also been applied in the late-stage modification of complex drug and natural product derivatives with high levels of enantioselectivity.