Regioselective Approach to β-Peroxyl Alcohols and Ethers from Alkenes.

A different regioselective three-component reaction of alkenes, oxygen sources, and hydroperoxides mediated by ammonium iodine to α-oxyperoxidates has been developed. Mechanistic studies demonstrated that regioselective radical addition and subsequent S N 2 nucleophilic substitution were possible for the formation of products. In addition to the traditional pathway of S N 2 reaction, that is, where nucleophiles attack the α-C atoms at the back side, an additional unusual transition configuration with the H 2 O molecule attacking the α-C atom at the front side was obtained.