Cross‐Coupling of Gaseous Alkanes with (Hetero)Aryl Bromides via Dual Nickel/Photoredox Catalysis

Abstract

Gaseous alkanes represent the most abundant carbon‐based chemical feedstocks in our planet. However, the intrinsic inertness of their C‐H bonds has rendered the use of these alkanes very difficult for purposes beyond aerobic combustion and energy intensive processes. Thus, clean and energy‐efficient transformations for their use in synthetic organic chemistry are still rare. Here we report a catalytic methodology for the direct cross‐coupling of gaseous alkanes with (hetero)aryl bromides through the combination of metallaphotoredox‐mediated hydrogen atom transfer and nickel catalysis. This protocol provides an efficient platform for the addition of short alkyl groups into diverse (hetero) aromatic rings, providing a wide range of high‐value alkyl(hetero)arenes, and bypassing the longstanding need of using preactivated alkylating agents in C(sp2)‐C(sp3) cross‐couplings. The method features high chemoselectivity, regioselectivity and a remarkable functional group tolerance, operates under mild conditions, and exhibits operational simplicity