Organo-photoredox-Catalyzed Selective Mono- and Bis-C–H Alkylation of Electron-Rich (Hetero)Arenes

Herein, we disclose a simple strategy for the C–H alkylation of electron-rich (hetero)arenes with alkyl bromides employing visible-light-mediated organo-photocatalytic SET processes. The generality of this method has been evidenced by the inclusion of a variety of alkyl radicals (α-alkyl-carbonyl, benzyl, cyanomethyl) as well as diverse biologically active electron-rich arenes and (hetero)arenes under mild conditions. The extent of alkylation with alkyl bromides was found to be controlled by introducing Zn(OAc)2 as a bromide scavenger, ensuring the blocking of potential bromo-arene byproduct formation under photoredox conditions. In addition, a sequential C–H alkylation strategy for selective bis-alkylation has also been developed via chronological incorporation of different alkyl radical precursors in one pot quite efficiently.