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(sp(2))=C(sp(2))-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.

Automated summary

An unprecedented electrochemical oxidative carbon-atom difunctionalization of isocyanides has been developed, providing a series of novel multisubstituted imino sulfide ethers. This metal-free and external oxidant-free method shows high stereoselectivities, excellent functional-group tolerance, and good efficiency for large-scale synthesis, enabling further derivatization of the products.