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| - A Doubly Destabilized Antiaromatic Cyclopentadienyl Cation: Solvolysis of a 5-Trifluoroacetoxy-5-heptafluoropropyl1,3-Cyclopentadiene1a
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| - The 5-trifluoroacetoxy-5-heptafluoropropylcyclopentadiene 15 rearranges to the isomeric trifluoroacetate 16 with a rate constant 5 × 105 less than that for solvolysis of the corresponding 5-CH3derivative 5. Labeling of 15 with 18O shows the rearrangement occurs by a [1,5]-sigmatropicrearrangement. Solvolysis of 16 occurs at a rate 4 times slower than its formation from 15 andleads to the extensively rearranged fulvene 18, implicating formation of the doubly destabilizedcation 20. Carbocation formation from 15 is retarded by a factor of 1020 relative to the model 11,showing cumulative destabilizing effects due to formation of the antiaromatic cyclopentadienylcarbocation and electron withdrawal by the fluoroalkyl group.
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