Deoxygenative C(sp ³ )–S Cross-Coupling of Alcohols and Sulfenamides

Sulfilimines, characterized by the unique -S(IV)═N- motif, are important scaffolds in medicinal and synthetic chemistry. While conventional syntheses typically rely on organohalides or pseudohalides as electrophiles, the direct use of alcohols remains challenging and underdeveloped. Herein, we report a metal-free, Ph₃P/ICH₂CH₂I-mediated deoxygenative C(sp³)-S cross-coupling between alcohols and sulfenamides. This method proceeds without preactivation of the alcohol, employs inexpensive reagents, and provides efficient access to sulfilimines, thereby offering a practical advance in sulfur functionalization that utilizes alcohols as electrophilic coupling partners.