A novel synthetic method for γ-acetoxy-( E)-α,β-unsaturated esters by the palladium catalyzed regio- and stereoselective acetoxylation of β,γ-unsaturated esters

Abstract

A new synthetic method for γ-acetoxy-α,β-unsaturated esters by the acetoxylation of β,γ-unsaturated esters catalyzed by PdCl 2 in the presence of KOAc and pentyl nitrite in acetic acid is presented. The reaction takes place at γ-position of the esters regioselectively with double bond migration to α,β-position. The E configuration of the double bond was confirmed by NMR analysis. Preliminary investigation to synthesize pyrenophorin and pyrenophorol using this reaction is described.