Hock Rearrangement

Abstract

This reaction is protic or Lewis acid–promoted rearrangement of hydroperoxides that have unsaturated unit(s) attached to the carbon bearing the hydroperoxide group to oxycarbonium ion, which undergoes nucleophilic attack by water, leading to the cleavage of C‐C bond and the formation of two carbonyl compounds and is generally referred to as the Hock rearrangement or Hock cleavage. This reaction also occurs in the absence of an added acid and even at temperatures substantially below room temperature. It has been reported that depending on the substrate structure and the choice of Lewis acid, dialkyl peroxide and ozonides might decompose via Hock rearrangement path. This reaction has been applied in the degradation of long hydrocarbon chains with unsaturated unit(s) into carbonyl compounds.

Connecting the “Dots”: From Free Radical Lipid Autoxidation to Cell Pathology and Disease

“… In a first mechanism, a Hock rearrangement of an acidified hydroperoxide is followed by hydrolysis. This textbook organic chemistry reaction generally requires strong acids or elevated temperatures − but may have niche importance under certain biological conditions, e.g. in lysosomes.…”