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

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.

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 Creators:
Gulzar, Naeem1, Author              
Jones, Kevin Mark2, Author              
Konnerth, Hannelore3, Author
Breugst, Martin3, Author
Klussmann, Martin2, Author              
Affiliations:
1Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445585              
2Research Group Klußmann, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445608              
3Univ Cologne, Dept Chem, D-50939 Cologne, Germany, ou_persistent22              

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Free keywords: computational chemistry; kinetics; nitrogen heterocycles; peroxides; reaction mechanisms
 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.

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Language(s): eng - English
 Dates: 2015-02-16
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.201405376
 Degree: -

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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: - Volume / Issue: 21 (8) Sequence Number: - Start / End Page: 3367 - 3376 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058