Photocatalytic decyanative radical addition based on cyano group transfer mediated by amine-ligated boryl radicals

Photocatalytic radical generation from non-special functional groups and molecules has become pivotal in the assembly of complex carbon scaffolds. Nitriles are valuable and ubiquitous building blocks in organic chemistry. However, their high C−CN bond dissociation energy and negative reduction potentials prevent them from serving as radical precursors. Herein, we describe a photocatalytic strategy for decyanative radical addition enabled by amine-ligated boryl radicals. This cyano group transfer strategy facilitates the generation of α-heteroatom methyl radicals from acetonitrile derivatives, facilitating the hydrofunctionalization of styrenes. The broad applicability of this method is demonstrated by its successful application in the late-stage functionalization of pharmaceuticals and bioactive compounds.