Transition-Metal-Catalyzed Hydroaminocarbonylations of Alkenes and Alkynes

While the amide bond is one of the most widespread backbones in natural peptides, pharmaceuticals, and agrochemicals, the atom-economic synthesis of amides remains a major challenge in organic chemistry. In this context, transition-metal-catalyzed hydroaminocarbonylation of cost-effective alkenes and alkynes has emerged as an ideal approach to access amides. However, it is only in recent times that more chemo- and regioselective hydroaminocarbonylation transformations, covering large substrate scope and under milder conditions, have been reported. In this review, we highlight some recent contributions to this field and elucidate the impact of ligands on regioselectivity, as well as discuss the potential applications of abundantly available nitrogen sources for hydroaminocarbonylation. Catalytic hydroaminocarbonylation of cost-effective alkenes or alkynes is a step- and atom-economical as well as waste-free method for synthesis of amides.The efficient palladium catalysts set the stage for catalytic hydrocarbonylation reaction with broad substrate scope and good chemo- and regioselectivity.The development of efficient strategies to overcome the basicity barrier imparted by the amines is key for obtaining good reactivity and selectivity.Through appropriate choice of different ligands and amine sources, branched or linear amides can be afforded, respectively.