Visible Light‐Induced Arylation/Alkylation/Phosphorylation of Isocyanides <i>via</i><scp>EDA</scp> Complex Activation

Comprehensive Summary Herein, it is reported that the aryl radicals derived from aryl thianthrenium salts are used as coupling partner in the arylation reactions of isocyanides, simultaneously as initiators for the formation of alkyl and phosphoryl radicals from ethers and diarylphosphine oxides. This cascade cyclization reaction leads to diverse arylated, alkylated and phosphorylated heteroaromatic compounds. Notably, this transformation can be achieved without the aid of metals or photocatalysts, exhibiting a wide substrate applicability and operational simplicity. Mechanistic studies suggest the involvement of radical processes and electron donor‐acceptor (EDA) complexes in this transformation.