Diastereoselective α‑Sulfenylation of <i>N</i>-<i>tert</i>-Butanesulfinyl Imidates

A diastereoselective α-sulfenylation of chiral α-aryl/alkyl N-tert-butanesulfinyl imidates has been developed. Suitable sulfur electrophiles can be used as sulfenylating reagents to intercept aza-enolates generated from imidate deprotonation, giving α-thiofunctionalized imidates in good yields with high diastereocontrol. This protocol for C–S bond formation can efficiently synthesize enantioenriched 1,2-sulfanyl amine derivatives such as sulconazole.