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Volumn 50, Issue 17, 2011, Pages 3882-3887

Molecular basis of elansolid biosynthesis: Evidence for an unprecedented quinone methide initiated intramolecular diels-alder cycloaddition/ macrolactonization

Author keywords

biosynthesis; intramolecular Diels Alder reaction; macrocyclizations; polyketides; quinone methides

Indexed keywords

BIOSYNTHETIC GENE CLUSTER; DEHYDRATION REACTIONS; DIELS-ALDER; DIELS-ALDER CYCLOADDITIONS; FEEDING EXPERIMENTS; INTRAMOLECULAR DIELS-ALDER REACTION; MACROCYCLIZATIONS; MACROLACTONIZATION; MODEL SUBSTRATES; MOLECULAR BASIS; POLYKETIDE METABOLITES; POLYKETIDES; QUINONE METHIDE; QUINONE METHIDES;

EID: 79954622948     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201006880     Document Type: Article
Times cited : (79)

References (31)
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    • R. Jansen, K. Gerth, H. Steinmetz, S. Reinecke, W. Kessler, A. Kirschning, R. Müller, unpublished results
    • R. Jansen, K. Gerth, H. Steinmetz, S. Reinecke, W. Kessler, A. Kirschning, R. Müller, unpublished results.
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    • Additionally, the presence of the alkyne group paves the way for a biomimetic total synthesis approach
    • Additionally, the presence of the alkyne group paves the way for a biomimetic total synthesis approach.
  • 14
    • 79954579794 scopus 로고    scopus 로고
    • Throughout the text atom numbering refers to the numbering of in the natural product elansolid
    • Throughout the text atom numbering refers to the numbering of in the natural product elansolid.
  • 15
    • 79954593371 scopus 로고    scopus 로고
    • note
    • To the best of our knowledge no examples of IMDA cycloadditions with a tertiary alcohol in allylic position to the diene have been described so far. In simpler cases, the stereoinduction of this center varies from moderate to excellent, see
  • 19
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    • 1H NMR spectrum of the corresponding ester
    • 1H NMR spectrum of the corresponding ester
  • 24
    • 79954582304 scopus 로고    scopus 로고
    • We had to choose an oxidation method that works well at temperatures as low as -30°C because the intermediate aldehyde spontaneously underwent an IMDA reaction at 0°C to yield tetrahydroindanes 27a, b as diastereomers (1:1) resulting from both endo transition states TS-I and TS-II.
    • We had to choose an oxidation method that works well at temperatures as low as -30°C because the intermediate aldehyde spontaneously underwent an IMDA reaction at 0°C to yield tetrahydroindanes 27a, b as diastereomers (1:1) resulting from both endo transition states TS-I and TS-II.
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    • 0019125839 scopus 로고
    • The p-TMS substituent was chosen as an alternative, because it can be transferred readily into a phenolic OH group
    • The p-TMS substituent was chosen as an alternative, because it can be transferred readily into a phenolic OH group:, R. L. Funk, K. P. C. Vollhardt, J. Am. Chem. Soc. 1980, 102, 5253-5261.
    • (1980) J. Am. Chem. Soc. , vol.102 , pp. 5253-5261
    • Funk, R.L.1    Vollhardt, K.P.C.2
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    • Instead, only deprotection of the PMB ether was observed
    • Instead, only deprotection of the PMB ether was observed.
  • 27
    • 79954587865 scopus 로고    scopus 로고
    • note
    • This high propensity to cyclization can be explained by 1) a low-energy LUMO of the dienophile, 2) a high-energy HOMO of the diene on account of conjugation to the alkyne, and 3) a double Thorpe-Ingold effect caused by the gem-dimethyl group and the tertiary alcohol. However, the gene analysis shown in Scheme 2 almost excludes the possibility of an IMDA precursor bearing a keto group at C25.
  • 28
    • 79954608167 scopus 로고    scopus 로고
    • See the Supporting Information for details on the analytical assignments
    • See the Supporting Information for details on the analytical assignments.
  • 30
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    • noteworthy, when the weaker acid AcOH in dioxane was employed instead, no IMDA products could be detected
    • noteworthy, when the weaker acid AcOH in dioxane was employed instead, no IMDA products could be detected.
  • 31
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    • note
    • While this manuscript was under review, Piel and co-workers disclosed a biosynthetic proposal for the elansolids, suggesting a rearranged allyl benzyl alcohol (similar to 6) as the direct substrate for the IMDA reaction. From our perspective, the electronic requirements for the IMDA cycloaddition are fulfilled only when the quinone methide moiety is involved as the key biosynthesis intermediate:, R. Teta, M. Gurgui, E. J. N. Helfrich, S. Künne, A. Schneider, G. Van Echten-Deckert, A. Mangoni, J. Piel, ChemBioChem 2010, 11, 2506-2512.
    • (2010) ChemBioChem , vol.11 , pp. 2506-2512
    • Teta, R.1    Gurgui, M.2    Helfrich, E.J.N.3    Künne, S.4    Schneider, A.5    Van Echten-Deckert, G.6    Mangoni, A.7    Piel, J.8


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.