Cycloadditions of Benzynes with the Azoxy [RN═N(O)R'] 1,3-Dipole Tautomer of 1-Hydroxybenzotriazole (HOBT).

Org Lett

Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, United States.

Published: July 2024

1,3-Dipolar cycloadditions of azoxy species are rare. HOBT exists as a pair of tautomers, one of which contains an azoxy subunit. We show that heavily substituted, thermally generated benzynes react with HOBT by engaging the azoxy tautomer to give products having a benzotriazole with a benzyne-derived -hydroxyaryl group at N2. DFT calculations were used to probe aspects of the mechanism. HOBT analogs of the uronium family (HBTU, HCTU, TATU, and HATU) react in an analogous fashion. The parent 1,2-dehydrobenzene (-benzyne) generated by the action of (basic) CsF reacts with HOBT in an orthogonal manner to give, exclusively, an N1-arylated product.

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http://dx.doi.org/10.1021/acs.orglett.4c01819DOI Listing

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