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Experimental and Computational Studies on the CH Amination Mechanism of Tetrahydrocarbazoles via Hydroperoxides
Author(s) -
Gulzar Naeem,
Jones Kevin Mark,
Konnerth Hannelore,
Breugst Martin,
Klussmann Martin
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405376
Subject(s) - tautomer , chemistry , enamine , imine , amination , allylic rearrangement , protonation , computational chemistry , hydrogen peroxide , density functional theory , photochemistry , reaction mechanism , aniline , catalysis , medicinal chemistry , organic chemistry , ion
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.