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Volumn 50, Issue 1, 2011, Pages 304-309

The leiodolide B puzzle

Author keywords

Homogeneous catalysis; marine natural products; NMR spectroscopy; structure elucidation; total synthesis

Indexed keywords

HOMOGENEOUS CATALYSIS; MARINE NATURAL PRODUCTS; NMR SPECTROSCOPY; STRUCTURE ELUCIDATION; TOTAL SYNTHESIS;

EID: 78650702670     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201005850     Document Type: Article
Times cited : (66)

References (55)
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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.
    • 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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    • 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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    • 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
    • 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 configuration of the newly formed alcohol center was confirmed by applying the modified Mosher method to both isomers; see, I. Ohtani, T. Kusumi, Y. Kashman, H. Kakisawa, J. Am. Chem. Soc. 1991, 113, 4092-4096.
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    • Bromide 24 was not sufficiently reactive to alkylate the benzyl lithium reagent derived from oxazole 39.
    • Bromide 24 was not sufficiently reactive to alkylate the benzyl lithium reagent derived from oxazole 39.
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    • More basic fluoride sources also cleave the TIPS ether and cause epoxide formation by intramolecular substitution of the adjacent bromide.
    • 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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    • 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
    • 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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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.