Three-component tandem benzyl-C(sp ³ )–H functionalization <i>via</i> thermally generated arynes with phenazine

A rare strategy for three-component tandem benzyl-C(sp³)-H functionalization <i>via</i> thermally generated arynes with phenazine without a catalyst was developed for the first time. A series of novel fused <i>N</i>,<i>N</i>'-disubstituted dihydrophenazine derivatives were synthesized with excellent yield and high atomic utilization. Deuterium-labelling studies suggested that the formation of carboanion intermediates has a significant role in the reaction. Our data enrich the field of C(sp³)-H functionalization and promote the development of aryne chemistry.