Harnessing the Intrinsic Reactivity of 2‐Cyano‐Substituted Heteroarenes to Achieve Programmable Double Alkylation

Herein, we report our study of tertiary radicals, generated through visible light decarboxylation, alkylating 2‐cyanoarenes through radical cross‐coupling at the ipso‐ or the para‐ positions of the cyano groups. Synthesis of a variety of α‐tertiary amines containing quaternary centers is described. The approach enables regioselective sequential double alkylation on either 2‐cyanopyridine or 2‐cyanopyrimidine with high efficiency. Our report illustrates the synthetic utility of α‐heteroatom‐substituted tertiary radicals in the synthesis of substituted heteroarenes.