Photochemical and electrochemical transformations involving isocyanides

Abstract

Isocyanides have long occupied a central position in organic synthesis due to their distinctive electronic structure and exceptional versatility, finding extensive applications in combinatorial chemistry and medicinal chemistry. Their capacity to rapidly generate molecular complexity has made isocyanide-based transformations particularly valuable for the assembly of bioactive molecules and architecturally complex natural products. Despite these advantages, many classical isocyanide reactions rely on stoichiometric reagents, harsh conditions, or multistep protocols, which limit their sustainability and broader applicability. In this context, photochemical and electrochemical strategies have emerged as powerful and environmentally benign alternatives for activating isocyanides. By exploiting light or electricity as traceless reagents, these approaches enable the controlled generation of reactive intermediates under mild conditions, often with high atom economy and broad functional group tolerance. Such features address long-standing challenges in isocyanide chemistry and align closely with the principles of green chemistry. Consequently, photo- and electrocatalytic transformations involving isocyanides have substantially expanded the repertoire of sustainable synthetic methodologies and opened new avenues for reaction design in drug discovery and materials science. This review provides a critical overview of photochemical and electrochemical isocyanide transformations reported between 2020 and 2025, with a focus on underlying mechanistic paradigms, key reactivity modes, and representative synthetic applications.