Electrochemical Oxidative Carbon‐Atom Difunctionalization: Towards Multisubstituted Imino Sulfide Ethers

Ethers (C−O/S) are ubiquitously found in a wide array of functional molecules and natural products. Nonetheless, the synthesis of imino sulfide ethers, containing an N(sp2)=C(sp2)−O/S fragment, still remains a challenge because of its sensitivity to acid. Developed here in is an unprecedented electrochemical oxidative carbon‐atom difunctionalization of isocyanides, providing a series of novel multisubstituted imino sulfide ethers. Under metal‐free and external oxidant‐free conditions, isocyanides react smoothly with simple and readily available mercaptans and alcohols. Importantly, the procedure exhibited high stereoselectivities, excellent functional‐group tolerance, and good efficiency on large‐scale synthesis, as well as further derivatization of the products. An unprecedented electrochemical oxidative carbon‐atom difunctionalization of isocyanides has been developed and it provides a series of novel multisubstituted imino sulfide ethers. Under metal‐free and external‐oxidant‐free conditions, isocyanides react smoothly with simple and readily available mercaptans and alcohols.