Electrochemical Transition Metal Hydride Catalysis

Abstract Transition metal hydride catalysis has emerged as a versatile tool for developing new bond‐disconnection strategies in synthetic chemistry. Conventional approaches to generate the key transition metal hydride species, however, remain constrained by their dependence on the use of stoichiometric hydride donors (e.g., hydrosilanes, borohydrides) and frequently require relatively complex reaction conditions. As a complementary and attractive alternative, electrochemically generated transition metal hydrides have recently been demonstrated to be catalytically effective intermediates for achieving similar synthetic purposes, employing electrons as the redox agents in a more practical and sustainable manner. This Concept introduces electrochemical transition metal hydride catalysis in the alkene functionalization and the synthesis of alkenes from alkyl radicals, providing an overview of recent advances, current limitations, and prospective future directions in this emerging field.