Transition-metal-catalyzed regiodivergent sulfonylation of aziridrines for the synthesis of β-amino sulfones†

β-Amino sulfones find extensive applications in pharmaceuticals, natural products, agrochemicals, and organic synthesis. Meanwhile, aziridine units are recognized as valuable intermediates in contemporary synthetic chemistry for efficient synthesis of β-functionalized amines through ring-opening reactions. However, the ring-opening sulfonylation of aziridines via SO₂ insertion, granting access to β-amino sulfones, remains unexplored. In this paper, we present a novel transition-metal-catalyzed system for the first regiodivergent sulfonylation of aziridines using SO₂ insertion to produce β-amino sulfones successfully. This method is distinguished by its mild reaction conditions, a broad substrate scope, ease of execution, and exceptional regioselectivity.