Cu-Amidobis(phosphine)-Catalyzed Direct Amidation of Unactivated Alkanes via C(sp)-H Activation.

Herein, we describe an acid-base-free, sustainable, and efficient method for direct amidation of unactivated alkanes and toluene derivatives, using the dimeric Cu complex [Cu{-PhPCHCONCHPPh-}] (here onward referred to as [PNP-Cu]). Using this method, C(sp)-N bond formation was achieved through the activation of very challenging C(sp)-H bonds in cycloalkanes, alkenes, allyl groups, and benzyl groups, with tolerance toward ketonic groups, heterocycles, and halide functionalities. One of the precatalysts, (PNHP-Cu-Npht) was isolated and structurally characterized.

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

Herein, we present a Cu-dimer, [Cu{PhPCHC(O)NCHPPh-}], which catalyzed direct C(sp)-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.

Copper(I) Complexes of Amide Functionalized Bisphosphine: Proximity Enhanced Metal-Ligand Cooperativity and Its Catalytic Advantage in C()-H Bond Activation of Unactivated Cycloalkanes in Dehydrogenative Carboxylation Reactions.

The reactions of amide functionalized bisphosphine, -PhPCHC-(O)N(H)CHPPh- () (BalaHariPhos), with copper salts is described. Treatment of with CuX in a 1:1 molar ratio yielded chelate complexes of the type [CuX{(-PhPCHC(O)N(H)CHPPh-)}-κ] (X = Cl, ; Br, ; and I, ), which on subsequent treatment with KOBu resulted in a dimeric complex [Cu(-PhPCHC(O)(N)CHPPh-)] (). Interestingly, complexes - showed weak N-H···Cu interactions.