title: Experimental and computational studies on the C-H amination mechanism of tetrahydrocarbazoles via hydroperoxides.
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.
authors: Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany).
authors: Naeem
authors: N
authors: Gulzar
authors: Kevin Mark
authors: KM
authors: Jones
authors: Hannelore
authors: H
authors: Konnerth
authors: Martin
authors: M
authors: Breugst
authors: Martin
authors: M
authors: Klussmann
keywords: computational chemistry; kinetics; nitrogen heterocycles; peroxides; reaction mechanisms