Rh-catalyzed alkene oxidation:: a highly efficient and selective process for preparing N-alkoxysulfonyl aziridines

Unique alkoxysulfonyl aziridine heterocycles were prepared through selective intra- and intermolecular alkene oxidation reactions. These methods are general and perform efficiently at low Rh-catalyst loadings (1-2 mol %) with only a slight excess of an inexpensive commercial oxidant, PhI(OAc)(2). For intermolecular processes, trichloroethylsulfamate was identified as a novel and markedly effective N-atom source, allowing reactions to be conducted with limiting amounts of the olefin substrate. The aziridine products submit to facile, nucleophilic ring opening; these processes are regioselective and can be used to prepare polyfunctionalized amines, including alpha-aminoketones via the direct addition of Me2SO. (c) 2006 Elsevier Ltd. All rights reserved.