Hydroxylamine-Derived Reagent as a Dual Oxidant and Amino Group Donor for the Iron-Catalyzed Preparation of Unprotected Sulfinamides from Thiols

An iron catalyzed reaction for the selective transformation of thiols (-SH) to sulfinamides (-SONH2) by a direct transfer of -O and free -NH2 groups has been developed. The reaction operates under mild conditions using a bench stable hydroxylamine derived reagent, exhibits broad functional group tolerance, is scalable and proceeds without the use of any precious metal catalyst or additional oxidant. This novel, practical reaction leads to the formation of two distinct new bonds (S=O and S-N) in a single step to chemoselectively form valuable, unprotected sulfinamide products. Preliminary mechanistic studies implicate the role of the alcoholic solvent as an oxygen atom donor.

Automated summary

An iron catalyzed reaction has been developed for the selective transformation of thiols to sulfinamides by a direct transfer of -O and free -NH2 groups. It operates under mild conditions, exhibits broad functional group tolerance, and does not require precious metal catalysts or additional oxidants. Preliminary mechanistic studies suggest the role of the alcoholic solvent as an oxygen atom donor.