Synthesis of α-(Nitroaryl)benzylphosphonates via Oxidative Nucleophilic Substitution of Hydrogen in Nitroarenes

Carbanions of diethyl benzylphosphonate and diethyl 1-phenylethylphosphonate add to nitroarenes to form relatively long-lived sigma(H) adducts that can be oxidized to products of oxidative nucleophilic substitution of hydrogen. By variation of the conditions, o- and p-nitroarylated derivatives of the starting phosphonates can be synthesized regioselectively. It has been proven that addition of carbanions of diethyl benzylphosphonate and diethyl 1-phenylethylphosphonate to nitroarenes is a fast process and the respective sigma(H) adducts are formed almost quantitatively.