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 alpha-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 alpha-C atoms at the back side, an additional unusual transition configuration with the H2O molecule attacking the alpha-C atom at the front side was obtained.

Automated summary

A different regioselective three-component reaction of alkenes, oxygen sources, and hydroperoxides mediated by ammonium iodine to alpha-oxyperoxidates has been developed. Mechanistic studies showed that regioselective radical addition and subsequent S(N)2 nucleophilic substitution can lead to the formation of products. In addition to the traditional pathway of S(N)2 reaction, an unusual transition configuration involving H2O attacking the alpha-C atom at the front side was also observed.