An auxiliary-assisted, copper catalyzed or promoted sulfenylation of benzoic acid derivative beta-C-H bonds and benzylamine derivative gamma-C-H bonds has been developed. The method employs disulfide reagents, copper(II) acetate, and DMSO solvent at 90-130 degrees C. Application of this methodology to the direct trifluoromethylsulfenylation of C-H bonds was demonstrated.