posted on 2024-02-26, 15:05authored byRufai Madiu, Erin L. Doran, Jenna M. Doran, Ali A. Pinarci, Kiran Dhillon, Dominic A. Rivera, Amari M. Howard, James L. Stroud, Dylan A. Moskovitz, Steven J. Finneran, Alyssa N. Singer, Morgan E. Rossi, Gustavo Moura-Letts
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.