Platinum-Electrocatalyzed Divergent Nitrile Cross-Coupling

There has been a significant progress in developing electrocatalytic hydrogenation procedures based on well-defined molecular complexes in recent years. However, active molecular catalysts typically require sophisticated ligands and complex reaction conditions. This report demonstrates that platinum chloride is an efficient catalyst precursor (without ligands) for divergent nitrile cross-coupling reactions. In this reactivity, nitriles act as ambiphilic reagents and selectively couple with nucleophiles (i.e., amines) or electrophiles (i.e., chloroformates). A broad range of structurally diverse secondary and tertiary amines, as well as organic carbamates, can be synthesized with high selectivity using the developed protocol. Mechanistic studies indicate that platinum nanoparticles are likely the active catalytic species. The proposed strategy offers a unique, modular, and divergent platform for electroreductive upgrading of feedstock nitriles.