Light-induced Pd catalyst enables C(sp2)–C(sp2) cross-electrophile coupling bypassing the demand for transmetalation

Transition metal-catalysed cross-coupling is a versatile tool for the construction of (hetero)biaryl scaffolds. However, the cross-electrophile coupling using abundant (hetero)aryl halides and pseudohalides is still in its infancy. In particular, a robust and general method for the cross-electrophile coupling would allow unparalleled entry into the vast collection of commercially available, structurally diverse (hetero)aryl halides and pseudohalides as coupling partners. Here we demonstrate a ligand-controlled visible light-driven mono-metallic cross-electrophile coupling platform in which the synergistic operation of a dual palladium catalytic cycle differentiates the electrophiles based on the bond dissociation enthalpy. This method is mild and selective and displays efficacy towards a wide range of functional groups and challenging heteroaryls. The power of the transformation has been revealed through the synthesis of (hetero)biaryl cores of various pharmaceuticals and diversification of peptides. Bypassing the traditional transmetalation step, this technology enables a general strategy for the cross-electrophile coupling of (hetero)aryl halides and pseudohalides. The direct cross-electrophile coupling of (hetero)aryl halides and pseudohalides is challenging. Now this reaction is facilitated by a visible light-induced palladium catalytic system that differentiates the reactants on the basis of the bond dissociation enthalpy affording unsymmetrical (hetero)biaryls.