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78650692277
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The original publication contains two inconsistent spellings, "leiodelide" and "leiodolide". We use the "olide" nomenclature to denote the macrolide character of these metabolites.
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The original publication contains two inconsistent spellings, "leiodelide" and "leiodolide". We use the "olide" nomenclature to denote the macrolide character of these metabolites.
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5
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78650689512
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Degradation studies proved the S configuration at C28 in leiodolide A. Interestingly, however, small amounts of the 28R epimer were also detected, suggesting that the biosynthetic formation of this remote center may not be stereospecific.
-
Degradation studies proved the S configuration at C28 in leiodolide A. Interestingly, however, small amounts of the 28R epimer were also detected, suggesting that the biosynthetic formation of this remote center may not be stereospecific.
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6
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78650688159
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The THF ring of 2 shows remote resemblance to the core region of amphidinolide X and Y, two macrolides that were previously the subjects of total synthesis and a molecular editing exercise in our laboratory
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The THF ring of 2 shows remote resemblance to the core region of amphidinolide X and Y, two macrolides that were previously the subjects of total synthesis and a molecular editing exercise in our laboratory
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More basic fluoride sources also cleave the TIPS ether and cause epoxide formation by intramolecular substitution of the adjacent bromide.
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One possibility is that the α-hydroxy-α-methyl carboxylic acid terminus in 2 is R rather than S configured (see Ref. [4]), although it is not clear that this change would have an impact on the chemical shift of so many remote C atoms. Likewise, Table 1 shows both olefinic regions as "hotspots", but the chemical shift differences are not large enough to suggest misassigned geometries.
-
One possibility is that the α-hydroxy-α-methyl carboxylic acid terminus in 2 is R rather than S configured (see Ref. [4]), although it is not clear that this change would have an impact on the chemical shift of so many remote C atoms. Likewise, Table 1 shows both olefinic regions as "hotspots", but the chemical shift differences are not large enough to suggest misassigned geometries.
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46
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78650709584
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1H NMR spectrum of leiodolide B depicted in the Supporting Information of the isolation paper clearly shows the presence of an impurity (ca. 5-10 %).
-
1H NMR spectrum of leiodolide B depicted in the Supporting Information of the isolation paper clearly shows the presence of an impurity (ca. 5-10 %).
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For other total syntheses from our research group which led to the revision of the originally proposed structures of bioactive natural products, see
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