CuI-amidobis(phosphine) catalyzed C(sp3)-C(sp3) direct homo- and hetero-coupling of unactivated alkanes via C(sp3)-H activation.

Herein, we present a CuI-dimer, [CuI{Ph2PC6H4C(O)NC6H4PPh2-o}]2, which catalyzed direct C(sp3)-H homocoupling of benzyl and cycloalkane derivatives with excellent yields and regio-selectivity. The method is very simple and tolerates various functionalities. Synergistic metal-ligand cooperativity was observed in Cu-N bond cleavage and protonation of nitrogen, and facilitates a bifunctional pathway, minimising the free energy corrugation for catalytic intermediates.