Novel Reaction of Tertiary Cyclopropanols

Abstract

The reaction of tertiary cyclopropanol silyl ethers with diethylaminosulfur trifluoride usually causes ring opening to produce allylic fluorides. However, cyclopropyl silyl ethers bearing a strong electron-donating substituent at C1 or an electron-withdrawing substituent at C2 do not afford allylic fluorides but fluorocyclopropanes. It has also been proved that an electron-donating substituent at C2 of the tertiary cyclopropanol silyl ethers promotes ring opening in the reaction with diethylaminosulfur trifluoride.Tertiary cyclopropanol systems react with a catalytic amount of vanadyl acetylacetonate under an oxygen atmosphere to afford β-hydroxy ketones and β-diketones. This reaction proceeds through peroxides. The peroxides could be effectively obtained from the reaction in 2,2,2-trifluoroethanol.