- Extension of the Criegee Rearrangement: Synthesis of Enol Ethers from Secondary Allylic Hydroperoxides
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The Criegee rearrangement has been extended to secondary allylic hydroperoxides, allowing for the selective synthesis of cyclic and acyclic enol ethers; the effect of base and electrophilic agent was studied.
- Goodman, Richard M.,Kishi, Yoshito
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p. 5125 - 5127
(2007/10/02)
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- Vinyl ether hydrolysis.XVII. Oxacyclonon-2,8-diene and the question of the unorthodox reaction mechanism for 9-methoxyoxacyclonon-2-ene
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The acid-catalyzed hydrolysis of the nine-membered ring cyclic vinyl ether, oxacyclonon-2,8-diene, occurs with a normal isotope effect, kH(1+)/kD(1+)=1.94, which indicates that this reaction proceeds by the conventional vinyl ether hydrolysis mechanism involving rate-determining proton transfer to carbon.The specific rate of this reaction, kH(1+)=3.9E-3 1/M 1/s, may then be used to show that there is no significant ring-size effect on the rate of hydrolysis of a vinyl ether group in a nine-membered ring.The previously noted unusually great reactivity of the vinyl ether group in 9-methoxyoxacyclonon-2-ene, for which an unorthodox reaction mechanism has been claimed, must therefore be due to some other cause.
- Burt, R. A.,Chiang, Y.,Kresge, A. J.,Szilagyi, S.
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