Vinyl ether hydrolysis. XIII. The failure of I-strain to produce a change in rate-determining step
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Rates of hydrolysis of 1-ethoxy-3,3,5,5-tetramethylcyclopentene and 1-methoxy-2,3,3,5,5-pentamethylcyclopentene measured in mineral acid and formic and acetic acid buffer solutions show general acid catalysis and give large kinetic isotope effects in the normal direction (kH/kD > 1). This indicates that these reactions proceed by the conventional mechanism for vinyl ether hydrolysis in which proton transfer from the catalyzing acid to the substrate is rate-determining, and that the I-strain in these substrates is insufficiently great to shift the reaction mechanism to rapidly reversible substrate protonation followed by rate-determining hydration of the ensuing cationic intermediate.
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1987 ◽
pp. 581-584
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1984 ◽
Vol 106
(23)
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pp. 7140-7143
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1972 ◽
pp. 2203
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1972 ◽
pp. 2180-2185
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2015 ◽
Vol 93
(4)
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pp. 463-467
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2004 ◽
Vol 17
(67)
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pp. 560-566
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1990 ◽
Vol 112
(16)
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pp. 5996-5998
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