The Baeyer-Villiger Oxidation of 8-Oxabicyclo[3.2.1]octan-3-ones. Substituent Effects on the Regioselectivity

Abstract 8-Oxabicyclo[3.2.1]octan-3-one derivatives serve as excellent models that elucidate factors controlling the reactivities and selectivities in the Baeyer-Villiger oxidation. The regioselectivity of the oxidation with trifluoroperacetic acid is markedly affected by the electronic properties of substituents at position α or β to the carbonyl function. Remote effects of the γ-substituents are also of significance. This study has disclosed yet unrecognized through-bond electronic influence and regioselection based on chiral orientation of hydroxyl group in the transient tetrahedral intermediate.