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Volumn 12, Issue 5, 2010, Pages 980-983

Total synthesis and determination of the absolute configuration of (-)-idesolide

Author keywords

[No Author keywords available]

Indexed keywords

IDESOLIDE; SPIRO COMPOUND;

EID: 77749254947     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol9029676     Document Type: Article
Times cited : (21)

References (34)
  • 2
    • 67849092818 scopus 로고    scopus 로고
    • For leading references, see: a
    • For leading references, see: (a) Snyder, S. A.; Kontes, F. J. Am. Chem. Soc. 2009, 131, 1745.
    • (2009) J. Am. Chem. Soc , vol.131 , pp. 1745
    • Snyder, S.A.1    Kontes, F.2
  • 8
    • 0000675159 scopus 로고    scopus 로고
    • Dimerization of α-hydroxy ketones: (a) Creary, X.; Rollin, A J. J. Org. Chem. 1977, 42, 4226.
    • Dimerization of α-hydroxy ketones: (a) Creary, X.; Rollin, A J. J. Org. Chem. 1977, 42, 4226.
  • 12
    • 33750011223 scopus 로고    scopus 로고
    • Isolation of methyl l-hydroxy-6-oxo-2-cyclohexenecarboxylate: (a) Rasmussen, B.; Nkurunziza, A.-J.; Witt, M.; Oketch-Rabah, H. A.; Jaroszewski, J. W.; Sterk, D. J. Nat. Prod 2006, 69, 1300.
    • Isolation of methyl l-hydroxy-6-oxo-2-cyclohexenecarboxylate: (a) Rasmussen, B.; Nkurunziza, A.-J.; Witt, M.; Oketch-Rabah, H. A.; Jaroszewski, J. W.; Sterk, D. J. Nat. Prod 2006, 69, 1300.
  • 16
    • 65249189478 scopus 로고    scopus 로고
    • AZADO : (a) Tomizawa, M.; Shibuya, M.; Iwabuchi, Y. Org. Lett. 2009, 11, 1829.
    • AZADO : (a) Tomizawa, M.; Shibuya, M.; Iwabuchi, Y. Org. Lett. 2009, 11, 1829.
  • 21
    • 77749239293 scopus 로고    scopus 로고
    • 99.5% ee of (+)-7 was obtained in 44% yield after 24 h reaction under the same conditions, together with 77% ee of (+)-ketone 8 in. 54% yield. Oxidation of the highly enantiomerically enriched (+)-7 gave (-)-8 which was converted to unnatural idesolied (+)-1 (see the Supporting Information).
    • 99.5% ee of (+)-7 was obtained in 44% yield after 24 h reaction under the same conditions, together with 77% ee of (+)-ketone 8 in. 54% yield. Oxidation of the highly enantiomerically enriched (+)-7 gave (-)-8 which was converted to unnatural idesolied (+)-1 (see the Supporting Information).
  • 26
    • 77749282236 scopus 로고    scopus 로고
    • This diastereomer dissociated to the monomer 2 during silica gel column chromatography. Although we could not isolate the diastereomer, we obtained a mixture of the diastereomer and idesolide after gel filtration chromatography. The 13C NMR spectrum (see the Supporting Information) indicated that this diastereomer is the epimer at the ketal carbon
    • 13C NMR spectrum (see the Supporting Information) indicated that this diastereomer is the epimer at the ketal carbon.
  • 27
    • 77749257532 scopus 로고    scopus 로고
    • AZADO-catalyzed dimerization of racemic monomer 2 gave racemic idesolide (rac-1) along with the diastereomer (diastereomer- Rac) consisting of (R)-2 and (S)-2. The structure of this diastereomer was confirmed by X-ray crystallography (see the Supporting Information). (Chemical Equetion Presentation)
    • AZADO-catalyzed dimerization of racemic monomer 2 gave racemic idesolide (rac-1) along with the diastereomer (diastereomer- Rac) consisting of (R)-2 and (S)-2. The structure of this diastereomer was confirmed by X-ray crystallography (see the Supporting Information). (Chemical Equetion Presentation)
  • 28
    • 77749239292 scopus 로고    scopus 로고
    • 19 brought about 45% ee (see the Supporting Information).
    • 19 brought about 45% ee (see the Supporting Information).
  • 29
    • 4143062549 scopus 로고    scopus 로고
    • In light of the experimental results that the dimerization was promoted either by tertiary alkylamines or tertiary amine N-oxide, we speculate AZADO behaved as a possible general base, Chemical Equetion Presentation For hydrogen-bonding interactions between stable nitroxyl radical and ROH, see: (a) Morishima, I, Ishihara, K, Tomishima, K, Inubushi, T, Yonezawa, T. J. Am. Chem. Soc. 1975, 97, 2749
    • In light of the experimental results that the dimerization was promoted either by tertiary alkylamines or tertiary amine N-oxide, we speculate AZADO behaved as a possible general base. (Chemical Equetion Presentation) For hydrogen-bonding interactions between stable nitroxyl radical and ROH, see: (a) Morishima, I.; Ishihara, K.; Tomishima, K.; Inubushi, T.; Yonezawa, T. J. Am. Chem. Soc. 1975, 97, 2749.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.