Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 12, Pages 6419-6424Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202016895
Keywords
[5+2] cycloaddition; benzoxepine; C− H activation; electrochemistry; electrooxidative annulation
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Funding
- DFG (Gottfried-Wilhelm-Leibniz award)
- Alexander von Humboldt Foundation
- CSC
- Projekt DEAL
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The study introduces the first electrochemical metal-catalyzed [5+2] cycloadditions, assembling seven-membered benzoxepine skeletons with a high substrate scope and efficiency. The mechanistic studies support a rhodium(III/I) regime involving a benzoxepine-coordinated rhodium(I) sandwich complex as the catalyst resting state.
Electrooxidative annulations involving mild transition metal-catalyzed C-H activation have emerged as a transformative strategy for the rapid construction of five- and six-membered heterocycles. In contrast, we herein describe the first electrochemical metal-catalyzed [5+2] cycloadditions to assemble valuable seven-membered benzoxepine skeletons by C-H/O-H activation. The efficient alkyne annulation featured ample substrate scope, using electricity as the only oxidant. Mechanistic studies provided strong support for a rhodium(III/I) regime, involving a benzoxepine-coordinated rhodium(I) sandwich complex as the catalyst resting state, which was re-oxidized to rhodium(III) by anodic oxidation.
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