Theoretical study on the concerted catalysis of Ir/Ni for amino radical transfer for C(sp2)–C(sp3) bond formation†

Thomas C. Maier's group has reported a synergistic Ir/Ni catalysis method for the synthesis of C(sp²)–C(sp³) bonds through an amino radical transfer (ART) strategy to generate alkyl radicals. This work employed density functional theory (DFT) to investigate the reaction mechanism, including the redox mechanism of Ir complexes in the generation process of amino radicals, analyzed the role and rationale behind alkyl boronic esters becoming dominant reaction pathways in the ART process, and discussed the competitive reaction mechanisms between oxidative addition and radical capture during C(sp²)–C(sp³) cross-coupling with Ni complexes. Through this theoretical calculation study, we aim to provide a theoretical foundation for constructing key carbon radical intermediates using ART and Ni-complex catalyzed free-radical-involved C(sp²)–C(sp³) cross-coupling reactions.