NMR Studies and electrophilic properties of triphenylphosphine–trifluoromethanesulfonic anhydride; a remarkable dehydrating reagent system for the conversion of aldoximes into nitriles

Abstract

The electrophilic properties of triphenyl(trifluoromethylsulfonyloxy)phosphonium trifluoromethanesulfinate and its corresponding bis(triphenyl)oxodiphosphonium trifluoromethanesulfinate dimer system have been exploited in the development of a mild method for converting aldoximes into nitriles. NMR Studies on the reaction of triphenylphosphine with various amounts of triflic anhydride at 0 °C is described. The reagent structure resulting from mixing 1.3 equiv of Ph 3 P with Tf 2 O (1.0 mmol) has been established as an equilibrium mixture consisting mainly of triphenyl(trifluoromethylsulfonyloxy)phosphonium trifluoromethanesulfinate and the corresponding bis(triphenyl)oxodiphosphonium trifluoromethanesulfinate dimer. The electrophilic properties of the system have been exploited in the development of a mild method for converting aldoximes into nitriles. The dehydration occurs at 0 °C under very mild conditions by initial activation of the oxime oxygen, followed by treatment with a base and subsequent elimination of triphenylphosphine oxide. The substrate scope and functional group tolerance of this useful method are explored.