The rate of rearrangement of 2-vinylcyclobutanol was studied in dimethyl sulfoxide and tetrahydrofuran solvents. Rearrangement to 3-cyclohexenol in 1% aqueous DMSO is catalyzed by lithium hydroxide. When lithium bromide is added to this medium, the rate is diminished by a factor of 17, due to the effect of added lithium cation on the ion-pairing equilibrium. Disappearance of the potassium salt (E isomer) in THF at -22 degrees C shows first-order behavior over four half-lives, but the first-order rate constant varies inversely with starting alkoxide concentration, suggesting that an ion pair dissociation equilibrium precedes rearrangement. The rearrangement of the potassium salt in 10:1 THF/HMPA is accelerated ii-fold over the rate in pure THF, due to specific solvation of the cation by HMPA. At 2 degrees C in THF the sodium salt of (Z)-2-vinylcyclobutanol epimerizes to the E isomer at a rate 36-fold faster than the E alkoxide rearranges to the product. The potassium (E)-2-(2-propenyl)cyclobutoxide salt rearranges 17 times slower than potassium 2-vinylcyclobutoxide, in agreement with a previous comparison of rates of fragmentations of homoallylic alkoxides. Secondary deuterium kinetic isotope effect (kie) measurements were made by rearranging mixtures of deuterated and nondeuterated potassium vinylcyclobutoxides at 0 degrees C in diethyl ether and analyzing the extent of reaction by GC and the isotopic content of the mixture by proton NMR. The large normal kie (k(H)/k(D2) = 1.34 +/- 0.04) at the terminal vinyl positions and the small normal kie at the carbinol position (k(H)/k(D) = 1.12 +/- 0.06) are explainable if an allyl anion/aldehyde intermediate species is formed. Ab initio calculations suggest that such an intermediate can exist in several possible conformations and should be nearly as stable in the gas phase as the starting vinylcyclobutoxide.