Synthesis of N‑Tosyl Allylic Amines from Substituted Alkenes via Vanadoxaziridine Catalysis

Herein, we report the catalytic allylic amination of α-methylalkenes with V₂O₃Dipic₂(HMPA)₂ and chloramine T as the quantitative source of N. The reaction works with high yields and stereoselectivities for α-methylalkenes. A proposed tosylnitrene-free catalytic cycle involving the formation of vanadoxaziridine complex 1 as the active catalyst and aminovanadation across the substrate as the rate-determining step has been proposed. Initial kinetic and competition experiments provide evidence for the proposed mechanism.