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 Cu^I-dimer, [Cu^I{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. [ABSTRACT FROM AUTHOR]