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Conventional diazo\u2010 and nitrene\u2010based aziridinations rely on hazardous precursors, tolerate limited substrate diversity, and deliver stereochemical outcomes that are largely dictated by the geometry of the starting materials. Here we report an electrocatalytic cobalt\u2010catalyzed hydroamination that converts readily available allylic sulfonamides into cis\u20102,3\u2010disubstituted aziridines. Mechanistic experiments, together with density functional theory (DFT) analysis, support a model in which diastereoselectivity is established during solvent\u2010caged radical recombination rather than by the geometry of the starting alkene. The resulting cis\u2010aziridines also undergo predictable and synthetically useful derivatizations, highlighting their value as functional intermediates. This operationally simple and scalable protocol provides direct access to stereochemically enriched cis\u2010aziridines without recourse to diazo or nitrene chemistry.<\/jats:p>","DOI":"10.1002\/anie.4116549","type":"journal-article","created":{"date-parts":[[2026,3,20]],"date-time":"2026-03-20T12:06:51Z","timestamp":1774008411000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["cis\u2010Aziridines From Terminal Alkenes via Diastereoselective Intramolecular Electrocatalytic Hydroamination"],"prefix":"10.1002","volume":"65","author":[{"given":"Ahhyeon","family":"Choi","sequence":"first","affiliation":[{"name":"Department of Chemistry Pohang University of Science and Technology (POSTECH)  Pohang Republic of Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hyeonseo","family":"Kim","sequence":"additional","affiliation":[{"name":"Department of Chemistry Pohang University of Science and Technology 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