Oxidative generation of 1-nitroalkyl radicals and their addition reaction to olefins

1-Nitroalkyl radicals are generated by oxidation of potassium salt of 1-aci-nitroalkanes with ammonium hexanitratocerate(IV). When the oxidation is carried out in the presence of electron-rich olefins, such as silyl enol ethers, intermolecular addition of the radicals onto the olefins proceeds to afford beta-nitro ketones, which are further converted to alpha,beta-unsaturated ketones in high yield. Stereoselective construction of fused ring systems is achieved by intramolecular addition of 1-nitroalkyl radicals.