Metal-free reductive desulfurization of C-sp3-substituted thiols using phosphite catalysis

Abstract

Phosphines and phosphites are critical tools for non-metal desulfurative methodologies due to the strength of the P 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 S bond. An overarching premise in these methods has been that stoichiometric (or excess) P(iii) reagent is required for reactivity. Despite decades of research, a desulfurative process that is catalytic in phosphine/phosphite has not been reported. Here, we report the successful merging of two thermal radical processes: the desulfurization of unactivated and activated alkyl thiols and the reduction of P(v) = S to P(iii) by reaction with a silyl radical species. We employ catalytic trimethyl phosphite, catalytic azo-bis(cyclohexyl)nitrile, and two equivalents of tris(trimethylsilyl)silane as the stoichiometric reductant and sulfur atom scavenger. This method is tolerant of common organic functional groups and affords products in good to excellent yields.