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Volumn 67, Issue 1, 2011, Pages 216-227

Asymmetric syntheses of (+)-negamycin, (+)-3-epi-negamycin and sperabillin C via lithium amide conjugate addition

Author keywords

(+) 3 epi Negamycin; (+) Negamycin; Asymmetric synthesis; Lithium amide; Sperabillin C

Indexed keywords

ACETOACETIC ACID; AMIDE; DEXTRO 3 EPI NEGAMYCIN; DEXTRO NEGAMYCIN; ESTER; ETHYL 4 CHLOROACETOACETATE; LITHIUM N BENZYL N (ALPHA METHYLBENZYL) AMIDE; NEGAMYCIN; PSEUDOPEPTIDE; SPERABILLIN C; UNCLASSIFIED DRUG;

EID: 78649785647     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2010.10.067     Document Type: Article
Times cited : (31)

References (71)
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    • For the syntheses of related structures, see
    • For the syntheses of related structures, see
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    • I.C.I. Pharma, French Patent 2433508 A1 19800314, 1980.
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    • Harada, S.; Ono, H. Eur. Patent Appl., 1986, EP 206068.
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    • Harada, S.1    Ono, H.2
  • 51
    • 78649800766 scopus 로고    scopus 로고
    • We have previously shown that the doubly diastereoselective conjugate addition of lithium N-benzyl-N-(α-methylbenzyl)amide to a range of chiral α,β-unsaturated carbonyl compounds proceeds under the dominant stereocontrol of the lithium amide, for instance see
    • We have previously shown that the doubly diastereoselective conjugate addition of lithium N-benzyl-N-(α-methylbenzyl)amide to a range of chiral α,β-unsaturated carbonyl compounds proceeds under the dominant stereocontrol of the lithium amide, for instance see
  • 59
    • 78649775401 scopus 로고    scopus 로고
    • 3)r. The enantiomeric purities of compounds 12 and 21 were inferred from that of (R)-16
    • 3). The enantiomeric purities of compounds 12 and 21 were inferred from that of (R)-16.
  • 61
    • 78649777179 scopus 로고    scopus 로고
    • For previous syntheses of epi-negamycin 2, see Refs. 4e,g,5e. For previous syntheses of epi-negamycin trifluoroacetic acid salt 2·TFA, see Ref. 4l
    • For previous syntheses of epi-negamycin 2, see Refs. 4e,g,5e. For previous syntheses of epi-negamycin trifluoroacetic acid salt 2·TFA, see Ref. 4l.
  • 62
    • 78649793123 scopus 로고    scopus 로고
    • 1H NMR spectra of the crude reaction mixtures and the isolated products precluded a more accurate determination of the reaction diastereoselectivity and/or product diastereoisomeric ratio
    • 1H NMR spectra of the crude reaction mixtures and the isolated products precluded a more accurate determination of the reaction diastereoselectivity and/or product diastereoisomeric ratio.
  • 63
    • 78649779232 scopus 로고    scopus 로고
    • In the case of the Hegedus synthesis a common intermediate was also derivatised to (+)-negamycin 1, and in the case of the I.C.I. Pharma synthesis the C(3)-stereogenic centre within (-)-5-epi-negamycin 2 was derived from (R)-aspartic acid; their stereochemical assignments are therefore secure
    • In the case of the Hegedus synthesis a common intermediate was also derivatised to (+)-negamycin 1, and in the case of the I.C.I. Pharma synthesis the C(3)-stereogenic centre within (-)-5-epi-negamycin 2 was derived from (R)-aspartic acid; their stereochemical assignments are therefore secure.
  • 65
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    • 3-Aminopropanamidine dihydrochloride 29·2HCl was prepared in 25% overall yield from commercially available 3-aminopropionitrile fumarate via N-tosyl protection, ethanolysis, treatment with ammonia and deprotection. For a similar procedure, see: A. Pierdet, L. Nédélec, V. Delaroff, and A. Allais Tetrahedron 36 1980 1763
    • (1980) Tetrahedron , vol.36 , pp. 1763
    • Pierdet, A.1    Nédélec, L.2    Delaroff, V.3    Allais, A.4
  • 71
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    • 1H NMR spectrum of this compound were too broad to be assigned
    • 1H NMR spectrum of this compound were too broad to be assigned.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.