A convenient protocol for the smooth conversion of the resistant PO bond in phosphane oxides into a reactive PN bond of synthetically useful pyrazolylphosphonium salts is described. A highly charged, oxophilic, phosphorus-centered trication is employed and the reactions are conducted at room temperature with quantitative yields. The resulting pyrazolylphosphonium cations are valuable synthetic intermediates and are used for the synthesis of a variety of organophosphorus compounds. This represents a new approach towards the transformation of the rather inert phosphoryl group under very mild reaction and workup conditions and aims towards alternatives to existing reduction methods for phosphane oxide functionalization.
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