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33
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84888438601
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The mono-epoxides used in the final ring-opening step were a mixture of diastereomers
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The mono-epoxides used in the final ring-opening step were a mixture of diastereomers.
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84888433598
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A ratio of kHClO4/kDClO4 ∼ 1 was observed for the dehydration reaction of arene hydrate 8e. A rate constant of kDClO4 = 2.0 (± 0.2) × 10-4 s-1 was determined by 1H NMR spectroscopy for the reaction of 8a in 2.5 mM DClO4 in D2O solution. A rate constant of kHClO4 = 2.25 (± 0.08) × 10-4 s-1 can be calculated for reaction of 8a in 2.5 mM HClO 4 in H2O solution from the second order rate constant for acid-catalyzed dehydration kH = 0.0899 M-1s-1, thus giving a kHClO4/ kDClO4 of ~1.
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A ratio of kHClO4/kDClO4 ∼ 1 was observed for the dehydration reaction of arene hydrate 8e. A rate constant of kDClO4 = 2.0 (± 0.2) × 10-4 s-1 was determined by 1H NMR spectroscopy for the reaction of 8a in 2.5 mM DClO4 in D2O solution. A rate constant of kHClO4 = 2.25 (± 0.08) × 10-4 s-1 can be calculated for reaction of 8a in 2.5 mM HClO 4 in H2O solution from the second order rate constant for acid-catalyzed dehydration kH = 0.0899 M-1s-1, thus giving a kHClO4/ kDClO4 of ~1.
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35
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84888432210
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Preliminary calculations using Gaussian 2003 B3Lyp6-31g* level of theory have shown that the presence of the hydroxyl group in the carbocation formed from diols 4 results in puckering of the two saturated carbons relative to the diene, whereas the hydrate carbocation centre is co-planar with the diene.
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Preliminary calculations using Gaussian 2003 B3Lyp6-31g* level of theory have shown that the presence of the hydroxyl group in the carbocation formed from diols 4 results in puckering of the two saturated carbons relative to the diene, whereas the hydrate carbocation centre is co-planar with the diene.
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36
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84888428601
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Our preliminary calculations using Gaussian 2003 B3Lyp6-31g* level of theory have shown that the most stable conformation for all of the hydrates places the hydroxyl group in an axial position, thus permitting an 'aromatic' hyperconjugative interaction between the developing vacant carbocation p-orbital and one of the β-CH2 hydrogens in the ring.
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Our preliminary calculations using Gaussian 2003 B3Lyp6-31g* level of theory have shown that the most stable conformation for all of the hydrates places the hydroxyl group in an axial position, thus permitting an 'aromatic' hyperconjugative interaction between the developing vacant carbocation p-orbital and one of the β-CH2 hydrogens in the ring.
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38
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4243664295
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C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165-195.
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