Effect of steric bulk on the absolute reactivity of allene oxides.
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.
An efficient cyclopentenone formation via an allene oxide
A new and efficient cyclopentenone annulation reaction has been developed. The annulation involves the in situ epoxidation [tBuOOH, VO(acac)2] of vinyl allenes 1a-f to furnish cyclopentenones 2a-f in 40~70% yield. This reaction closely resembles the proposed biosynthetic route to prostanoids.
Syntheses of Seven‐ and Five‐Membered Rings from Allyl Cations
The cycloaddition of allyl cations to conjugated dienes offers an efficient and general tool for the construction of seven-membered carbocycles. The silver salt route is highly suitable for generating allyl cations and can be used even in most difficult cases, i. e. for elusive and intractable allyl cations such as 2-methylallyl, 2-methoxyallyl, and the parent allyl cation. Cycloadditions to the 2-methoxyallyl cation come very close to the prototype of a 6π, 7C reaction, since the carbonyl group introduced into the new ring can either be used for further transformations or be removed altogether. The combination of an allyl cation with π reactants, especially conjugated dienes, is a powerful and strongly convergent synthetic method since it permits one-step assembly, from a C3 and a C4 unit, of a cluster of up to four chiral centers in a ring which is larger than six-membered. Allyl cations combine with electron-rich 2π systems to form novel five-membered rings. The nature of the organometallic intermediates has been elucidated in many cases.