Intermolecular 2+2 imine-olefin photocycloadditions enabled by Cu(I)-alkene MLCT
Daniel Flores, Michael L. Neville, Valerie A. Schmidt
Abstract
2 + 2 Photocycloadditions are idealized, convergent construction approaches of 4-membered heterocyclic rings, including azetidines. However, methods of direct excitation are limited by the unfavorable photophysical properties of imines and electronically unbiased alkenes. Here, we report copper-catalyzed photocycloadditions of non-conjugated imines and alkenes to produce a variety of substituted azetidines. Design principles allow this base metal-catalyzed method to achieve 2 + 2 imine-olefin photocycloaddition via selective alkene activation through a coordination-MLCT pathway supported by combined experimental and computational mechanistic studies.
Topics & Concepts
AlkeneImineOlefin fiberIntermolecular forceChemistryCycloadditionCombinatorial chemistryConjugated systemPhotochemistryCatalysisOrganic chemistryMoleculePolymerSynthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsRadical Photochemical Reactions