Dehydrative Cross-Coupling for C–N Bond Construction under Transition-Metal-Free Conditions

A transition-metal-free catalytic system was designed to address the dehydrative cross-coupling of unactivated primary/secondary alcohols with amines/amides under environmentally benign conditions. Mg²⁺ and counteranion (PF₆^–) worked synergistically to realize C–OH bond cleavage and concomitant C–N bond formation. A wide range of allylic alcohols and amines/amides were tolerated well in this transformation, which allowed C–N bond construction with high efficiency.