Highly selective and additive-free Pd(OAc)2/CPP catalyzed hydroaminocarbonylation of alkynes†

Herein, the synthesis of branched α,β-unsaturated amides by a hydroaminocarbonylation reaction of alkynes with various amine substrates such as aromatic amines, aliphatic amines, solid amine sources like NH₄HCO₃, and even strongly basic piperidines is reported, using a Pd(OAc)₂/hybrid N-heterocyclic carbene–phosphine–phosphine (CPP) catalytic system. The reactions feature no additives, wide substrate scope, high selectivity (b/l > 99 : 1) and excellent yields. Mechanistic studies have disclosed that the reaction takes place via a palladium hydride pathway. CPP adopts a hybrid bidentate ligand conformation with a carbene–phosphine coordination mode, wherein one phosphorus atom remains externally accessible, potentially serving as a stabilizing auxiliary during catalytic cycles.