Abstract
Herein, we report the catalytic allylic amination of α-methylalkenes with V(2)O(3)Dipic(2)(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.