We report the mechanisms and factors controlling of the intramolecular C-H bond amination and double bond aziridination on various sulfamate esters, H2NSO2OR, catalyzed by dirhodium tetracarboxylate complexes: Rh2(H2O)(O2CH)4, Rh2(H2O)(AcO)4, and Rh2(H2O)(esp)2. We emphasize the competition between tertiary and benzylic amination, as well as between allylic amination and aziridination processes. Previously, these processes have been experimentally studied by Du Bois and co-workers, and a strong dependency on the catalyst employed has been reported (Tetrahedron 2009  , 65, 3042-3051 and references therein). The obtained good agreement between the theoretically and the experimental findings allowed us to assess the factors controlling of these reactions.

Mechanistic insight into the dirhodium tetracarboxylate catalyzed intramolecular C-H bond amination and double bond aziridination reactions on sulfamate esters

244th National Meeting (2012)

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