Migratory C(sp²)-H/C(sp³)-H Cross-Coupling Enabled by Metallaphotoredox Catalysis

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.