Rh-2(S-nap)(4), a chiral dirthodium tetracarboxamidate complex, has been developed and shown to be an effective catalyst for the asymmetric, intramolecular C-H amination of sulfamate esters. Enantiomeric excesses range from 60-99% for a collection of disparately substituted 3-arylpropylsulfamates. In addition, Rh-2(S-nap)(4) is found to promote chemoselective allylic C-H oxidation of unsaturated sulfamates, a property not observed with other dirhodium complexes tested to date.