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Experimental and Computational Studies on the C-H Amination Mechanism of Tetrahydrocarbazoles via Hydroperoxides

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Gulzar,  Naeem
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Jones,  Kevin Mark
Research Group Klußmann, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Klussmann,  Martin
Research Group Klußmann, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Gulzar, N., Jones, K. M., Konnerth, H., Breugst, M., & Klussmann, M. (2015). Experimental and Computational Studies on the C-H Amination Mechanism of Tetrahydrocarbazoles via Hydroperoxides. Chemistry – A European Journal, 21(8), 3367-3376. doi:10.1002/chem.201405376.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0026-CE8D-4
Abstract
The acid-catalyzed reactions of photochemically generated tetrahydrocarbazole peroxides with anilines have been studied experimentally and computationally to identify the underlying reaction mechanism. The kinetic data indicate a reaction order of one in the hydroperoxide and zero in the aniline. Computational investigations using density functional theory support the experimental findings and predict an initial tautomerization between an imine and enamine substructure of the primarily generated tetrahydrocarbazole peroxide to be the rate controlling step. The enamine tautomer then loses hydrogen peroxide upon protonation, generating a stabilized allylic carbocation that is reversibly trapped by solvent or aniline to form the isolated products.