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31
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0011260524
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3/MeOH, 95:5) gave diastereoisomeric mixture of syn and anti γ-aminoalcohols as pale yellow syrups.
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3/MeOH, 95:5) gave diastereoisomeric mixture of syn and anti γ-aminoalcohols as pale yellow syrups.
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0011260346
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note
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Abstract.
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35
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0011262436
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+] typical of a carbonyl compound rather than of an allyl alcohol.
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+] typical of a carbonyl compound rather than of an allyl alcohol.
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36
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0011343281
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In our opinion, the formation of an enol ester borohydride intermediate in analogy with the reported reductions of enaminoesters and β-hydroxybenzyl oximes cannot be invoked. This intermediate should transfer hydride to the carbon-carbon double bond, but this double bond appears electrophilic rather than nucleophilic. Alternatively boron could link in the α-position giving rise to a β-enaminoketone, whose reduction can occur either intramolecularly or intermolecularly as in the β-hydroxyketone system. Finally the water molecule, which seems to be present also in 'dry' cerium chloride could be the proton source which allows keto-enol tautomerism, followed by reduction of the β-enaminoketone. Intramolecular shift of a hydrogen atom from nitrogen to oxygen atom is discarded because reduction occurs also with N,N-dialkylamino derivatives (entry 8).
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In our opinion, the formation of an enol ester borohydride intermediate in analogy with the reported reductions of enaminoesters and β-hydroxybenzyl oximes cannot be invoked. This intermediate should transfer hydride to the carbon-carbon double bond, but this double bond appears electrophilic rather than nucleophilic. Alternatively boron could link in the α-position giving rise to a β-enaminoketone, whose reduction can occur either intramolecularly or intermolecularly as in the β-hydroxyketone system. Finally the water molecule, which seems to be present also in 'dry' cerium chloride could be the proton source which allows keto-enol tautomerism, followed by reduction of the β-enaminoketone. Intramolecular shift of a hydrogen atom from nitrogen to oxygen atom is discarded because reduction occurs also with N,N-dialkylamino derivatives (entry 8).
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