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 vanad...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 2024-03, Vol.89 (6), p.4001-4008
Main Authors: Madiu, Rufai, Doran, Erin L., Doran, Jenna M., Pinarci, Ali A., Dhillon, Kiran, Rivera, Dominic A., Howard, Amari M., Stroud, James L., Moskovitz, Dylan A., Finneran, Steven J., Singer, Alyssa N., Rossi, Morgan E., Moura-Letts, Gustavo
Format: Article
Language:English
Citations: Items that this one cites
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.3c02859