Effect of steric bulk on the absolute reactivity of allene oxides

Abstract

Alpha-alkyl substituted fluorenylidene allene oxides were generated photochemically from appropriately substituted fluorenol derivatives in 2,2,2-trifluoroethanol (TFE) in order to assess the affect of steric bulk on the absolute reactivity of the allene oxides. The absolute reactivities of the allene oxides were measured using nanosecond laser flash photolysis, and were found to change little in TFE upon going from alpha-methyl to alpha-butyl to alpha-t-butyl. However, all three alpha-alkyl substituted allene oxides were considerably more reactive than the alpha-hydrogen derivative, indicating that steric bulk did not result in a decrease in reactivity as is typically found in other allene oxides. The contrary reactivity of the fluorenylidene allene oxides is explained by examining in detail the reactions of these allene oxides, determined from product studies.