Cu I -amidobis(phosphine) catalyzed C(sp 3 )-C(sp 3 ) direct homo- and hetero-coupling of unactivated alkanes via C(sp 3 )-H activation.

Herein, we present a Cu I -dimer, [Cu I {Ph 2 PC 6 H 4 C(O)NC 6 H 4 PPh 2 - o }] 2 , which catalyzed direct C(sp 3 )-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.