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Volumn 121, Issue 23, 1999, Pages 5467-5480

Enantiodivergent total syntheses of (+)- and (-)-scopadulcic acid A

Author keywords

[No Author keywords available]

Indexed keywords

SCOPADULCIC ACID B;

EID: 0033575122     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990404v     Document Type: Article
Times cited : (154)

References (98)
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    • For recent reviews of the use of intramolecular Heck reactions in natural products total synthesis, see: (a) Link, J. T.; Overman, L. E. In Metal-Catalyzed Cross Coupling Reactions; Stang, P. J., Diederich, F., Eds.; Wiley-VCH: Weinheim, 1998; Chapter 6. (b) Link, J. T.; Overman, L. E. CHEMTECH 1998, 28 (8, August), 19-26.
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    • August
    • For recent reviews of the use of intramolecular Heck reactions in natural products total synthesis, see: (a) Link, J. T.; Overman, L. E. In Metal-Catalyzed Cross Coupling Reactions; Stang, P. J., Diederich, F., Eds.; Wiley-VCH: Weinheim, 1998; Chapter 6. (b) Link, J. T.; Overman, L. E. CHEMTECH 1998, 28 (8, August), 19-26.
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    • note
    • The scopadulan numbering system will be employed in the discussion of all synthetic intermediates. Correct IUPAC designations of intermediates are found in the Experimental Section.
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    • note
    • This erroneous assignment resulted in an incorrect specification of the relative stereochemistry at C6 of structures 10-13 in ref 20.
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    • note
    • 39c The absolute configuration for the levorotatory (1S,5R) enantiomer of 14 is incorrectly specified in refs 39a and 39c.
  • 51
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    • note
    • The authors have deposited coordinates for this derivative with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, U.K.
  • 52
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    • note
    • 37 to rationalize bimolecular cyclopropanations brought about with this catalyst correctly predicts the formation of (15,2R)-14.
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    • note
    • 46 followed by acetalization.
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    • 1H NMR analysis of the methyl mandelate derivative.
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    • Asymmetric reducing conditions recently described by Noyori and co-workers, which were published after this phase of our synthesis was completed, would appear to be particularly attractive for the synthesis of (R)-21: Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738-8739.
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    • note
    • When both enantiomers of an intermediate have been prepared, those in the series leading to unnatural (+)-SDA are specified with the ent designation. The preparation of 27, which is a precursor of natural (-)-SDA, is described in Scheme 8.
  • 80
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    • note
    • 20
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    • note
    • 56 (70) The enantiopurity of 33 should be at least 99.8%, since it derives from combination of fragments of 88 and >99% ee. Two factors, each of which alone would have been sufficient, dictate that there would have been no loss in enantiopurity in the conversion of 52→27: (a) the sample of 52 employed in the Cope rearrangement step contained no detectable C6 epimer, and (b) any (E)-enoxysilane produced upon enolization of 52 would not undergo Cope rearrangement at room temperature.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.