The inter- or intramolecular oxidative carboamination of alkynes catalyzed by [py2TiCl2NPh]2 is reported. These multicomponent reactions couple alkenes, alkynes and diazenes to form either α,β-unsaturated imines or α-(iminomethyl)cyclopropanes via a TiII/TiIV redox cycle. Each of these products is formed from a common azatitanacyclohexene intermediate that undergoes either β-H elimination or α,γ-coupling, wherein the selectivity is under substrate control.
Bibliographical noteFunding Information:
Financial support was provided by the University of Minnesota (start-up funds) and the National Institutes of Health (1R35GM119457). Equipment for the Chemistry Department NMR facility were supported through a grant from the National Institutes of Health (S10OD011952) with matching funds from the University of Minnesota.
© 2016 American Chemical Society.