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Intermolecular 2+2 imine-olefin photocycloadditions enabled by Cu(I)-alkene MLCT.

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.

SUBMITTER: Flores DM

PROVIDER: S-EPMC9120151 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Intermolecular 2+2 imine-olefin photocycloadditions enabled by Cu(I)-alkene MLCT.

Flores Daniel M DM Neville Michael L ML Schmidt Valerie A VA

Nature communications 20220519 1

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 ph ...[more]

PMID: 35589714

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