Site-selective bromination of sp(3) C–H bonds

A method for converting sp(3) C–H to C–Br bonds using an N-methyl sulfamate directing group is described. The reaction employs Rh(2)(oct)(4) and a mixture of NaBr and NaOCl and is performed in aqueous solution open to air. For all sulfamates examined, oxidation occurs with high selectivity at the γ-carbon, affording a uniquely predictable method for C–H bond halogenation. Results from a series of mechanistic experiments suggest that substrate oxidation likely proceeds by a radical chain process. Initial formation of an N-halogenated sulfamate followed by Rh-mediated homolysis generates an N-centered radical, which serves as the active oxidant.