Photocatalytic Decyanative Radical Addition Based on Cyano Group Transfer Mediated by Amine-Ligated Boryl Radicals

Herein, we describe a photocatalytic strategy for decyanative hydrofunctionalization of styrenes with α-heteroatom-substituted acetonitriles. This strategy facilitates the generation of α-heteroatom methyl radicals from acetonitriles through cyano group transfer (CGT) enabled by amine-ligated boryl radicals. The broad applicability of this method is demonstrated by its successful application in late-stage functionalization of bioactive compounds. Combined experimental and computational studies suggest that the strong nucleophilic character of amine-ligated boryl radical is beneficial in facilitating the CGT process.