DMD oxidation of in-situ-generated σH adducts derived from nitroarenes and the carbanion of 2-phenylpropionitrile to phenols:: The first direct substitution of a nitro by a hydroxy group

The dimethyldioxirane (DMD) oxidation of sigma(H) adducts derived from nitroarenes and the carbanion of 2-phenylpropionitrile yields unexpectedly the phenols 5 as the major products, while the usually observed nitroarenes 4 are formed in very little amounts, if any. The phenol yield was much improved when a small quantity (0.5-1.0 equiv.) of water was added at the start of the reaction. This novel oxidation of Meisenheimer complexes provides the first direct synthesis of phenols from nitroarenes, an unprecendented transformation.