A chemoselective
Staudinger reduction/sulfur­(VI) fluoride exchange
cascade has been developed to join two chemical segments through an
aryl sulfamate ester (RNH–SO<sub>2</sub>–OAr) linkage.
Aryl fluorosulfate is exploited in this work as the first tetrahedral
electrophilic trap for the in situ generated iminophosphorane. Ten
examples using azide-containing compounds are presented