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Only a few examples of malonate additions to benzocycloheptadienone dicarboxylate were reported by Fohlisch's group: Föhlisch, B, Schupp, E, Dukek, U, Graessle, I. Liebigs Ann. Chem. 1973, 1851
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Only a few examples of malonate additions to benzocycloheptadienone dicarboxylate were reported by Fohlisch's group: Föhlisch, B.; Schupp, E.; Dukek, U.; Graessle, I. Liebigs Ann. Chem. 1973, 1851.
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20
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60949097608
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Temporary TBS protection was required to avoid major loss of material due to the high water solubility of the deprotected form of 8
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Temporary TBS protection was required to avoid major loss of material due to the high water solubility of the deprotected form of 8.
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21
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0000483392
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24
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60949100987
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No reaction was observed at 80 °C.
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No reaction was observed at 80 °C.
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25
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60949104495
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Most of the bicyclic adducts existed as mixtures of two epimers due to the easily epimerizable center α to the nitrile, but this was of no consequence for later chemistry. Tricycles 12 and 14 were single isomers, as shown in Figure 1 for 12
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Most of the bicyclic adducts existed as mixtures of two epimers due to the easily epimerizable center α to the nitrile, but this was of no consequence for later chemistry. Tricycles 12 and 14 were single isomers, as shown in Figure 1 for 12.
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26
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60949090087
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The epimerization of 2 with Et3N is puzzling, bearing in mind that 2 is obtained from 14 as a single epimer from much more strongly basic conditions. We have no convincing rationale for this result but consider it possible that under the conditions used in Scheme 6 the configuration of the ester could be temporarily locked by formation of a lactone acetal (i, which is then opened by MeOH on work-up addition of solid NB 4Cl, Equation Presented
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4Cl). (Equation Presented)
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