Addition to electron deficient olefins of alpha-oxy carbon- centered radicals, generated from cyclic ethers and acetals by the reaction with alkylperoxy- lambda(3)-iodane.

Thermal decomposition of 1-tert-butylperoxy-1,2-benziodoxol-3(1H)-one in cyclic ethers and acetals at 50 degrees C generates alpha-oxy carbon-centered radicals, which undergo an addition reaction with vinyl sulfones and unsaturated esters.

Iodobenzene-catalyzed alpha-acetoxylation of ketones. in situ generation of hypervalent (diacyloxyiodo)benzenes using m-chloroperbenzoic acid.

Reported here for the first time is the iodobenzene-catalyzed alpha-oxidation of ketones, in which diacyloxy(phenyl)-lambda3-iodanes generated in situ act as real oxidants of ketones and m-chloroperbenzoic acid serves as a terminal oxidant. Oxidation of a ketone with m-chloroperbenzoic acid in acetic acid in the presence of a catalytic amount of iodobenzene, BF3.Et2O, and water at room temperature under argon affords an alpha-acetoxy ketone in good yield.