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Volumn 12, Issue 6, 2006, Pages 1736-1746

Total synthesis of gambierol: The generation of the A-C and F-H subunits by using a C-glycoside centered strategy

Author keywords

Gambierol; Giycosides; Metathesis; Natural products; Total synthesis

Indexed keywords

GAMBIEROL; GLYCOSIDES; METATHESIS; TOTAL SYNTHESIS;

EID: 32944480843     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200500993     Document Type: Article
Times cited : (89)

References (112)
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    • and references therein; d ciguatoxin CTX3C
    • c) hemibrevetoxin B: A. Zakarian, A. Batch, R. A. Holton, J. Am. Chem. Soc. 2003, 125, 7822, and references therein; d) ciguatoxin CTX3C:
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    • Zakarian, A.1    Batch, A.2    Holton, R.A.3
  • 16
  • 53
    • 32944476386 scopus 로고    scopus 로고
    • note
    • The analogous cycloaddition reaction between Danishefsky's diene and 15 proceeds in 95% ee and 65% yield, see ref. [20].
  • 54
    • 32944479086 scopus 로고    scopus 로고
    • note
    • In our previous report of this reaction, we erroneously reported that ent-18 produced 17, see ref. [17a].
  • 57
    • 32944478637 scopus 로고    scopus 로고
    • note
    • The enantiomeric excess of 17 was determined using a chiracel OD HPLC column.
  • 66
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    • note
    • 4] (see ref. [20]) or in 93% ee and 74% yield using 18.
  • 67
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    • note
    • We carried out DAFT calculations on the epoxidation of related sub-strates in an effort to better understand the relatively lower levels of selectivity in the epoxidation reactions of 21 and 23. The calculations indicated that both the level of asynchronicity of the formation of the C-O bonds and stereoelectronics were important. A. Orendt, S. W. Roberts, J. D. Rainier, unpublished results.
  • 80
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    • We had previously observed that the amount of cyclic product was dependent upon the steric shielding of the ester. Related reactions have been reported, see ref. [16] and a) J. R. Stille, R. H. Grubbs, J. Am. Chem. Soc. 1986, 108, 855;
    • (1986) J. Am. Chem. Soc. , vol.108 , pp. 855
    • Stille, J.R.1    Grubbs, R.H.2
  • 85
    • 0034710476 scopus 로고    scopus 로고
    • Both α- and β-C-glycosides can be generated from the corresponding anhydride by simply changing the nucleophile used, see ref. [16] and J. D. Rainier, J. M. Cox, Org. Lett. 2000, 2, 2707.
    • (2000) Org. Lett. , vol.2 , pp. 2707
    • Rainier, J.D.1    Cox, J.M.2
  • 86
    • 32944475067 scopus 로고    scopus 로고
    • note
    • Also unsuccessful were more conventional oxocarbenium ion couplings with allyl nucleophiles. For examples of this type of reaction, see refs. [28a-d]:
  • 88
    • 32944460194 scopus 로고    scopus 로고
    • note
    • Attempts to induce a related methyl migration failed.
  • 95
    • 32944465288 scopus 로고    scopus 로고
    • note
    • Presently, it is not clear why this reaction failed to give C-glycoside products. We have successfully coupled other tri- and tetracyclic anhydrides with allyl nucleophiles.
  • 96
    • 32944470283 scopus 로고    scopus 로고
    • note
    • We initially employed an ester having an acetal in place of the silyl ether. However, the Takai-Utimoto acyclic enol ether forming reaction with this substrate gave a substantial amount of eliminated material.
  • 103
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    • Subsequently, we showed that anhydride 78 underwent other coupling reactions with C-nucleophiles to give C-ketosides, see S. W. Roberts, J. D. Rainier, Org. Lett. 2005, 7, 1141.
    • (2005) Org. Lett. , vol.7 , pp. 1141
    • Roberts, S.W.1    Rainier, J.D.2
  • 104
    • 32944478491 scopus 로고    scopus 로고
    • A C(25) TIPS ether performed similarly to 77 while a C(25) TES ether gave mixtures of C(23) diastereomers similar to 83, see ref. [49]
    • A C(25) TIPS ether performed similarly to 77 while a C(25) TES ether gave mixtures of C(23) diastereomers similar to 83, see ref. [49].
  • 107
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    • For studies on the formation and reactivity of Fischer carbenes from enol ethers and 38, see a) J. Louie, R. H. Grubbs, Organometallics 2002, 21, 2153;
    • (2002) Organometallics , vol.21 , pp. 2153
    • Louie, J.1    Grubbs, R.H.2
  • 110
    • 32944465134 scopus 로고    scopus 로고
    • manuscript in preparation
    • Ab initio calculations were carried out at the DFT level: A. Orendt, S. A. Roberts, J. D. Rainier, manuscript in preparation.
    • Orendt, A.1    Roberts, S.A.2    Rainier, J.D.3
  • 111
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    • See reference [12k, 1]
    • See reference [12k, 1].


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.