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Volumn 46, Issue 46, 2007, Pages 8840-8844

Differentiation of nonconventional "carbanions" - The total synthesis of nemorosone and clusianone

Author keywords

Carbanions; Cyclization; Natural products; Total synthesis

Indexed keywords

CARBANIONS; CLUSIANONE; NEMOROSONE;

EID: 36749012899     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200703886     Document Type: Article
Times cited : (92)

References (35)
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    • Subsequent reports will describe the synthesis of the individual antipodes of garsubellin
    • D. R. Siegel, S. J. Danishefsky, J. Am. Chem. Soc. 2006, 128, 1048. Subsequent reports will describe the synthesis of the individual antipodes of garsubellin.
    • (2006) J. Am. Chem. Soc , vol.128 , pp. 1048
    • Siegel, D.R.1    Danishefsky, S.J.2
  • 8
    • 33845249441 scopus 로고    scopus 로고
    • A total synthesis of clusianone has recently appeared, see a
    • A total synthesis of clusianone has recently appeared, see a) V. Rodeschini, N. M. Ahmad, N. S. Simpkins, Org. Lett. 2006, 8, 5283;
    • (2006) Org. Lett , vol.8 , pp. 5283
    • Rodeschini, V.1    Ahmad, N.M.2    Simpkins, N.S.3
  • 10
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    • The steps which we employed were actually done independently before the appearance of the above report
    • c) P. Nuhant, M. David, T. Pouplin, B. Delpech, C. Marazano, Org. Lett. 2007, 9, 287. The steps which we employed were actually done independently before the appearance of the above report.
    • (2007) Org. Lett , vol.9 , pp. 287
    • Nuhant, P.1    David, M.2    Pouplin, T.3    Delpech, B.4    Marazano, C.5
  • 12
    • 36749016657 scopus 로고    scopus 로고
    • Attempts to execute the cross-metathesis with 2-methyl-2-butene resulted in formation of significant amounts of a disubstituted olefin side product. To avoid this undesired side reaction, 2-methylpropene was used in the cross-metathesis reaction;
    • a) Attempts to execute the cross-metathesis with 2-methyl-2-butene resulted in formation of significant amounts of a disubstituted olefin side product. To avoid this undesired side reaction, 2-methylpropene was used in the cross-metathesis reaction;
  • 19
    • 0033583729 scopus 로고    scopus 로고
    • For the earliest reported type of reaction in this general area, see a
    • For the earliest reported type of reaction in this general area, see a) K. C. Nicolaou, J. A. Pfefferkorn, S. Kim, H. X. Wei, J. Am. Chem. Soc. 1999, 121, 4724;
    • (1999) J. Am. Chem. Soc , vol.121 , pp. 4724
    • Nicolaou, K.C.1    Pfefferkorn, J.A.2    Kim, S.3    Wei, H.X.4
  • 22
    • 36749035266 scopus 로고    scopus 로고
    • It seems reasonable to assume that introduction of deuterium at the bridgehead is indicative of bridgehead deprotonation by the LDA. The alternative would be that the actual removal of the proton at C1 is somehow occurring during the CD3OD quenching process via some combination of secondary amine and secondary lithium amide
    • 3OD quenching process via some combination of secondary amine and secondary lithium amide.
  • 23
    • 0000332522 scopus 로고    scopus 로고
    • cf. inter alia; a N. G. Clemo and G. Pattenden, Tetrahedron Lett. 1982, 23, 585;
    • cf. inter alia; a) N. G. Clemo and G. Pattenden, Tetrahedron Lett. 1982, 23, 585;
  • 27
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    • see reference [5
    • d) see reference [5].
  • 28
    • 36749103117 scopus 로고    scopus 로고
    • At several stages of this study, the apparent deprotonation [13] and subsequent quenching of the bridgehead enolate with electrophiles is improved through the use of TMSCl. The reasons for this remain to be explored in detail
    • [13] and subsequent quenching of the bridgehead enolate with electrophiles is improved through the use of TMSCl. The reasons for this remain to be explored in detail.
  • 33
    • 36749003724 scopus 로고    scopus 로고
    • With nemorosone in hand, we found that it was both light-sensitive and air-sensitive. When nemorosone was dissolved in chloroform, a solution of fully synthetic nemorosone and chloroform had decomposed after a few days at room temperature. In fact, a solution of nemorosone in chloroform at -20°C is also significantly decomposed after a few days. We resorted to the use of ammonium formate because the original isolation was such that ammonium formate would have been present in the methanol solvent wherein the NMR spectrum of nemorosone was measured. Through this device, a stable spectrum was obtained
    • With nemorosone in hand, we found that it was both light-sensitive and air-sensitive. When nemorosone was dissolved in chloroform, a solution of fully synthetic nemorosone and chloroform had decomposed after a few days at room temperature. In fact, a solution of nemorosone in chloroform at -20°C is also significantly decomposed after a few days. We resorted to the use of ammonium formate because the original isolation was such that ammonium formate would have been present in the methanol solvent wherein the NMR spectrum of nemorosone was measured. Through this device, a stable spectrum was obtained.
  • 34
    • 36749044727 scopus 로고    scopus 로고
    • In addition to the proton spectrum, a 13C spectrum was also obtained on fully synthetic nemorosone. Infrared and mass spectra were all measured. These data are found in the Supporting Information
    • 13C spectrum was also obtained on fully synthetic nemorosone. Infrared and mass spectra were all measured. These data are found in the Supporting Information.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.