Migratory C(sp ² )–H/C(sp ³ )–H Cross‐Coupling Enabled by Metallaphotoredox Catalysis

Abstract Direct twofold C─H cross‐coupling between two readily available substrates offers a step‐ and atom‐economical alternative to traditional cross‐coupling reactions. Here we report the successful realization of this transformation through a dual catalytic platform that combines two orthogonal C─H activation modes: nickel‐catalyzed through‐space 1,4‐Ni/H shift and photoredox‐mediated hydrogen atom transfer (HAT). This synergistic strategy enables regio‐ and stereoselective synthesis of substituted alkenes or arenes from aryl bromides (or chlorides) and abundant alkanes with excellent chemo‐ and stereoselectivity. Mechanistic studies and DFT calculations indicate that HAT is the rate‐limiting step, while radical addition and subsequent reductive elimination collectively govern the observed regioselectivity.