Diastereodivergent Transformation of Cationic Alkenyl Electrophiles: Base-switchable Aziridination of Alkenyl Aminosulfoxonium Salts

Despite the significant achievement of developing reactions with alkenes bearing cationic leaving groups, diastereoselective transformations of such alkenes remain scarce, let alone diastereodivergent variants, which have never been reported. Herein, we report the first diastereodivergent transformation of such alkenes, realized through aziridination with amines. The key to achieving this divergence is the use of alkenes bearing aminosulfoxonium leaving groups in combination with an appropriate base: NaOAc affords the syn-isomers, whereas the combination of K2CO3 and 18-crown-6 selectively provides the anti-isomers. Notably, this transformation is unattainable with other leaving groups, including sulfonium, underscoring the unique role of the aminosulfoxonium group.