Electrochemical Sulfenamide Synthesis Bypassing Gaseous Amines with Formamide Surrogates

A novel, transition metal- and oxidant-free electrochemical
method
has been developed for the synthesis of sulfenamides with high atom
economy (84.1%). This strategy employs commercially available N,N-dimethylformamide (DMF) and its derivatives
as liquid, safe, and convenient surrogates for low-boiling amines,
thereby overcoming the handling challenges associated with gaseous
amines such as dimethylamine. Under constant current conditions, a
variety of thiols and disulfides undergo efficient cross-coupling
with formamides to afford the corresponding sulfenamides in good to
excellent yields. The reaction features a broad substrate scope, excellent
functional group tolerance, mild conditions (50 °C, air atmosphere),
and simple workup without the need for column chromatography in many
cases. Gram-scale synthesis and preliminary mechanistic studies are
also presented, highlighting the practical utility and potential reaction
pathway of this sustainable electrocatalytic protocol.