Free radical chemistry. Part 3. Substituent effects in additions of ethers to fluorinated alkenes

Abstract

Systematic studies on free-radical additions of acyclic ethers to hexafluoropropene reveal the influence of steric effects on the competitive formation of mono-, di-, and tri-adducts. It is concluded that ‘capto-dative’ effects are not dominant in systems containing polyfluoroalkyl groups. Remarkably efficient free-radical additions of trialkyl borates, to fluorinated alkenes occur, but in a series X-OMe (X = MeCO, HCO, MeOCO etc.) reactivity is reduced by electron withdrawal.