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Volumn 47, Issue 52, 2008, Pages 10081-10085

Total synthesis of the marine diterpenoid blumiolide C

Author keywords

Medium sized rings; Metathesis; Natural products; Terpenoids; Total synthesis

Indexed keywords

CHEMICAL REACTIONS;

EID: 57749110637     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200804004     Document Type: Article
Times cited : (32)

References (38)
  • 1
    • 85055223076 scopus 로고    scopus 로고
    • Eds, G. M. Cragg, D. G. I. Kingston, D. J. Newman, CRC, Boca Raton, FL
    • a) Anticancer Agents from Natural Products (Eds.: G. M. Cragg, D. G. I. Kingston, D. J. Newman), CRC, Boca Raton, FL, 2005;
    • (2005) Anticancer Agents from Natural Products
  • 11
    • 57749084512 scopus 로고    scopus 로고
    • The Xenia diterpenoids of the xeniaphyllan class are based on the same core structure as the plant derived caryophyllans. For the recent first enantioselective synthesis of β-caryophellene see reference [6b]
    • The Xenia diterpenoids of the xeniaphyllan class are based on the same core structure as the plant derived caryophyllans. For the recent first enantioselective synthesis of β-caryophellene see reference [6b]
  • 13
    • 3343012187 scopus 로고    scopus 로고
    • For recent reviews on ring-closing olefin metathesis, see: a
    • For recent reviews on ring-closing olefin metathesis, see: a) R. H. Grubbs, Tetrahedron 2004, 60, 7117-7140;
    • (2004) Tetrahedron , vol.60 , pp. 7117-7140
    • Grubbs, R.H.1
  • 15
    • 57749100180 scopus 로고    scopus 로고
    • The RCM-based construction of monocyclic oxanonene systems has been reported, including structures with trisubstituted Z double bonds. See: a M. T. Crimmins, J. M. Ellis, J. Org. Chem. 2007, 72, 1649-1660;
    • The RCM-based construction of monocyclic oxanonene systems has been reported, including structures with trisubstituted Z double bonds. See: a) M. T. Crimmins, J. M. Ellis, J. Org. Chem. 2007, 72, 1649-1660;
  • 17
    • 57749106626 scopus 로고    scopus 로고
    • For the RCM-based construction of 10-membered carbocyclic rings, see: a M. Nevalainen, A. M. P. Koskinen, Angew. Chem. 2001, 113, 4184-4186;
    • For the RCM-based construction of 10-membered carbocyclic rings, see: a) M. Nevalainen, A. M. P. Koskinen, Angew. Chem. 2001, 113, 4184-4186;
  • 18
    • 0035813926 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2001, 40, 4060-4062;
    • (2001) Angew. Chem. Int. Ed , vol.40 , pp. 4060-4062
  • 31
    • 57749119445 scopus 로고    scopus 로고
    • In control experiments the two separated anomers of ketone 15 were treated with MeMgBr individually. For each anomer only one diastereoisomeric product was obtained in the addition reaction; however, the relative and absolute configuration of these products at C3 and C11 was not determined.
    • In control experiments the two separated anomers of ketone 15 were treated with MeMgBr individually. For each anomer only one diastereoisomeric product was obtained in the addition reaction; however, the relative and absolute configuration of these products at C3 and C11 was not determined.
  • 33
    • 57749118856 scopus 로고    scopus 로고
    • Aldehyde 19 was obtained from the known propargylic alcohol 22 (THP = tetrahydropyranyl; D. Díez Martín, I. S. Marcos, P. Basabe, R. E. Romero, R. F. Moro, W. Lumeras, L. Rodríguez, J. Urones, Synthesis 2001, 1013-1022) in a four step sequence comprising PMB-protection of the tertiary hydroxyl group, removal of the THP group with p-toluene sulfonic acid, REDAL reduction to the E alkene and TPAP oxidation in 55% overall yield. Details of the synthesis will be published elsewhere.
    • Aldehyde 19 was obtained from the known propargylic alcohol 22 (THP = tetrahydropyranyl; D. Díez Martín, I. S. Marcos, P. Basabe, R. E. Romero, R. F. Moro, W. Lumeras, L. Rodríguez, J. Urones, Synthesis 2001, 1013-1022) in a four step sequence comprising PMB-protection of the tertiary hydroxyl group, removal of the THP group with p-toluene sulfonic acid, REDAL reduction to the E alkene and TPAP oxidation in 55% overall yield. Details of the synthesis will be published elsewhere.
  • 34
    • 57749121958 scopus 로고    scopus 로고
    • [6b]
    • [6b]
  • 37
    • 57749099134 scopus 로고    scopus 로고
    • The 1H NMR spectrum of synthetic blumiolide C corresponds exactly with the published data.[9] For the 13C NMR spectrum of synthetic 1 17 out of 20 signals match with the literature data within 0.1 ppm. Two carbonyl signals deviate by 0.6 ppm, which could simply be a consequence of different measuring conditions, See the Supporting Information, For the signal at 130.3 ppm in our spectrum the corresponding literature signal is reported at 133.0 ppm. We assume this to be a publication error in reference [9, 1: HRMS: calc. for [M+Na, 353.1723, found 353.1728; lit. HRFABMS calc. for [M, 331.1902, found 331.1905, α]D25, 50.0° (c, 0.4 g cm-3, CHCl3, lit, α]D25, 66.0° c, 0.4 g cm-3, CHCl3
    • 3).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.