General Paradigm in Photoredox Ni-Catalyzed Cross-Coupling Allows for Light-Free Access to Reactivity.

We establish self-sustained Ni(I/III) cycles as a potentially general paradigm in photoredox Ni-catalyzed carbon-heteroatom cross-coupling reactions by presenting a strategy that allows us to recapitulate photoredox-like reactivity in the absence of light across a wide range of substrates in the amination, etherification, and esterification of aryl bromides, the latter of which has remained, hitherto, elusive under thermal Ni catalysis. Moreover, the accessibility of esterification in the absence of light is especially notable since previous mechanistic studies on this transformation under photoredox conditions have unanimously invoked energy transfer-mediated pathways.