PIFA-Promoted, Solvent-Controlled Selective Functionalization of C(sp2)–H or C(sp3)–H: Nitration via C–N Bond Cleavage of CH3NO2, Cyanation, or Oxygenation in Water

A novel nitration (via C(sp3)-N breaking/C(sp2)-N formation with CH3NO2) mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA) is described. The NO2 transfer from CH3NO2 to the aromatic group of the substrate is possible with careful selection of the solvent, NaX, and oxidant. In addition, the solvent-controlled C(sp2)-H functionalization can shift to an α-C(sp3)-H functionalization (cyanation or oxygenation) of the α-C(sp3)-H of cyclic amines.