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Updated: Sep 22, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Intermolecular 2+2 imine-olefin photocycloadditions enabled by Cu(I)-alkene MLCT
Daniel M Flores1,2, Michael L Neville1, Valerie A Schmidt3
1University of California San Diego, Department of Chemistry and Biochemistry, 9500 Gilman Drive, La Jolla, CA, 92093, USA.
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.
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