This review covers the recent progress in electro-/photo-catalytic alkene-derived radical cation chemistry for organic synthesis, including synthetic strategies, plausible mechanisms and further research outlook.

A cobalt­(III)-catalyzed directed C-7 alkynylation of indolines with easily accessible bromoalkynes has been developed. The reaction has a broad substrate scope with excellent yields and represents a powerful route to the synthesis of 7-alkynyl-substituted indolines. In addition, the reaction can be extended to the coupling of N-aryl 7-azaindoles, highlighting the synthetic practicability of the strategy.

The In(OTf)3-promoted three-component photoredox alkylarylation of styrenes with alkyl NHP esters and arenes to access alkylated arene derivatives through C–C bond cleavage and C–H functionalization is reported.