Gulzar, Naeem, Jones, Kevin Mark, Konnerth, Hannelore, Breugst, Martin ORCID: 0000-0003-0950-8858 and Klussmann, Martin ORCID: 0000-0002-9026-205X (2015). Experimental and Computational Studies on the C-H Amination Mechanism of Tetrahydrocarbazoles via Hydroperoxides. Chem.-Eur. J., 21 (8). S. 3367 - 3377. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3765

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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.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Gulzar, NaeemUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Jones, Kevin MarkUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Konnerth, HanneloreUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Breugst, MartinUNSPECIFIEDorcid.org/0000-0003-0950-8858UNSPECIFIED
Klussmann, MartinUNSPECIFIEDorcid.org/0000-0002-9026-205XUNSPECIFIED
URN: urn:nbn:de:hbz:38-412366
DOI: 10.1002/chem.201405376
Journal or Publication Title: Chem.-Eur. J.
Volume: 21
Number: 8
Page Range: S. 3367 - 3377
Date: 2015
Publisher: WILEY-V C H VERLAG GMBH
Place of Publication: WEINHEIM
ISSN: 1521-3765
Language: English
Faculty: Faculty of Mathematics and Natural Sciences
Divisions: Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
CARBON-HYDROGEN; COUPLING REACTIONS; REACTION ENERGIES; M06 SUITE; AB-INITIO; FUNCTIONALIZATION; AUTOXIDATION; BONDS; PHOTOOXYGENATION; TAUTOMERISMMultiple languages
Chemistry, MultidisciplinaryMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/41236

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