A Chiral Rhodium Carboxamidate Catalyst for Enantioselective C−H Amination

Rh2(S-nap)4, a chiral dirhodium 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, Rh2(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.