Experimental and computational studies on the C-H amination mechanism of tetrahydrocarbazoles via hydroperoxides.

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.