Circumventing Mukaiyama Oxidation: Selective S–O Bond Formation via Sulfenamide–Alcohol Coupling

A new method for synthesizing sulfinimidate esters through NBS-promoted oxidative coupling of sulfenamides with alcohols has been developed, offering a selective, efficient, and metal-free alternative to Mukaiyama-type oxidations. This approach uses inexpensive reagents, works under mild conditions, and is scalable to gram quantities. It is suitable for late-stage functionalization of complex alcohols, including bioactive molecules like RU58841, and accommodates chiral alcohols such as ʟ-menthol, producing diastereomeric sulfinimidate esters. These esters can undergo stereospecific Grignard substitutions, achieving up to 93% enantiomeric excess, highlighting their potential as intermediates for enantioselective S-C bond formation.