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12244294425
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note
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Because of the instability of the condensation products, rough purification was performed by rapid column chromatography on florisil gel.
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20
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12244267918
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note
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The Knoevenagel reaction of β-ketonitrile 13c with benzaldehyde and isobutyraldehyde afforded E-olefins selectively in 89% and 95% yields, respectively.
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21
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12244262191
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and references therein
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4-mediated hydration of nitriles has been reported to proceed under neutral conditions at 120 °C, but our nitrile 16 was decomposed under the literature conditions. Murahashi, S.; Sasao, S.; Saito, E.; Naota, T. J. Am. Chem. Soc. 1992, 57, 2521 and references therein.
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24
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12244288257
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note
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The stereochemistry of epoxyhydrofuran 20 was not determined.
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26
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12244279896
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note
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8
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27
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12244308989
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note
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8
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29
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12244306853
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note
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A probable mechanism for the Knoevenagel reaction is as follows: an ammonium salt reacts with an aldehyde to afford an imine, which then reacts with a nucleophile. The isomerization of imine and enamine is a well-known process, which leads to the racemic imine. For the above reaction mechanism, see the reviews in ref 11.
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30
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0010640653
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