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Volumn 32, Issue 36, 1991, Pages 4651-4654

Synthesis of (+)-dihydrocompactin and (+)-compactin via vinylsilane terminated cationic cyclization

Author keywords

benzenedimethanol acetal initiator; mevinic acid total synthesis; vinylsilane mediated cationic bicyclization

Indexed keywords

4A,5 DIHYDROCOMPACTIN; COMPACTIN; UNCLASSIFIED DRUG;

EID: 0025862355     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)92272-X     Document Type: Article
Times cited : (22)

References (51)
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    • For a detailed review of polyene cyclizations with acetal and non-acetal initiators, see, J.D. Morrison, Academic Press, New York
    • (1984) Asymmetric Synthesis , vol.3 , pp. 341
    • Bartlett1
  • 19
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    • The exceptional electrofugality of the silyl group directs elimination away from the more substituted position. See ref. 21.
  • 26
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    • Acetals of 1,2-benzenedimethanol have been previously prepared and used for carbonyl protection. See
    • (1985) J. Org. Chem. , vol.50 , pp. 5759
    • Smith1    Kruger2
  • 32
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    • Poor yields of the desired trans-allylic alcohol were obtained without first removing the silyl protecting group. This deprotection/reprotection was avoided by the alternative route (eq 2) using a benzyl ether.
  • 36
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    • For recent reviews of the Claisen rearrangement, see
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    • Ziegler1
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    • The Hetero-Cope Rearrangement in Organic Synthesis
    • (1989) Synthesis , pp. 71
    • Blechert1
  • 42
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    • We attribute the emergence of the axial CO bond in 7a and 7b to cyclization via the axially-oriented oxo-carbenium ion depicted in eq 1. The alternative orientation of the oxocarbenium residue suffers from a syn pentyl-type interaction with the equatorial alkoxymethyl substituent in the bicyclization transition state. Additional supporting data and discussion related to this observation will be presented elsewhere. For recent detailed discussions of mechanistic features of Lewis acid induced acetal substitution, see
    • (1990) J. Org. Chem. , vol.55 , pp. 6107
    • Mori1    Ishihara2    Flippin3    Nozaki4    Yamamoto5    Bartlett6    Heathcock7
  • 46
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    • Of the 38 kcal/mol of β-cation stabilization due to silicon, approximately one-fourth is due to inductive donation. Most of the effect is attributed to hyperconjugation, which requires a (Z)-vinylsilane in a chair-like cyclization transition state.
    • (1985) J. Am. Chem. Soc. , vol.107 , pp. 1496
    • Wierschke1    Chandrasekhar2    Jorgensen3
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    • 3 centers is then reversed relative to 7a and 7b.
    • (1990) Tetrahedron , vol.46 , pp. 2677
    • Lambert1
  • 51
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    • Yields cited in the Schemes and eq 2 are for chromatographically pure substances. All structural assignments are in accord with spectroscopic and analytical data.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.