A Rh(II)-catalyzed chemoselective oxidative amination and nucleophilic trapping of gem-dimethyl sulfamates has been presented. For 2,2-dimethyl-4-arylbut-3-yn-1-yl sulfamates, the reactions underwent a metallonitrene-initiated alkyne oxidation along with nucleophilic trapping of H2O upon oxidation, giving aroyl group containing heterocycles. For 2,2-dimethyl-4-arylpent-3-yn-1-yl sulfamates, the α-iminometal carbene intermediate was trapped by aryl group migration, delivering a styryl group containing heterocycles.