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Volumn 69, Issue 18, 2004, Pages 5993-6000

Enantioefficient synthesis of α-ergocryptine: First direct synthesis of (+)-lysergic acid

Author keywords

[No Author keywords available]

Indexed keywords

ENANTIOEFFICIENT SYNTHESIS; ERGOCRYPTINE; PEPTIDES; REACTION SEQUENCES;

EID: 4344703215     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049209b     Document Type: Article
Times cited : (63)

References (52)
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  • 4
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    • The Alkaloids; Brossi, A., Ed.; Acadenic Press; San Diego, CA; and citations therein
    • (b) Ninomiya, I.; Kiguchi, T. Ergot Alkaloids; The Alkaloids, Vol. 38; Brossi, A., Ed.; Acadenic Press; San Diego, CA, 1990; pp 1-156 and citations therein.
    • (1990) Ergot Alkaloids , vol.38 , pp. 1-156
    • Ninomiya, I.1    Kiguchi, T.2
  • 19
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    • note
    • (b) Although Goto's method has given a really short route to tetracyclic 4a and 4c, the application of the expensive and dangerous n-BuLi at -78°C can interfere with their scale-up preparation. In our modification powdered KOH was applied for deprotonation of 3 at 0°C. After acylation at room temperature, the obtained crude product was transformed directly to 4c in 43-46% overall yield.
  • 24
    • 4344650601 scopus 로고    scopus 로고
    • Moldvai, I.; Temesvári-Major, E.; Balázs, M.; Gács-Baitz, E.; Egyed, O.; Szántay, Cs. J. Chem. Res. (S) 1999, 687; J. Chem. Res. (M) 1999, 3018-3029.
    • (1999) J. Chem. Res. (M) , pp. 3018-3029
  • 26
    • 0015973611 scopus 로고
    • The first synthesis of racemic 7 has been performed via oxidation of the corresponding alcohol with the 2,3-dihydroindole ring. Only one characterization datum (mp 145-148°C) of (±)-7 has been described. See: Bach, N. J.; Hall, D. A.; Kornfeld, E. J. J. Med. Chem. 1974, 17, 312-314.
    • (1974) J. Med. Chem. , vol.17 , pp. 312-314
    • Bach, N.J.1    Hall, D.A.2    Kornfeld, E.J.3
  • 35
    • 0033534430 scopus 로고    scopus 로고
    • It is worth mentioning that Rapoport and co-workers published a method for synthesizing an advanced intermediate of the Ergot alkaloids, an optically active amino derivative of Uhle's ketone, following an entirely different route. Hurt, C. R.; Lin, R.; Rapoport, H. J. Org. Chem. 1999, 64, 225-233.
    • (1999) J. Org. Chem. , vol.64 , pp. 225-233
    • Hurt, C.R.1    Lin, R.2    Rapoport, H.3
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    • 4344696328 scopus 로고
    • Kollonitsch, J.; Hajós, A.; Kraut, M.; Gábor V. Acta Chim. Hung. 1955, 6, 381-395; Chem. Abstr. 1955, 49, 6872h.
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    • 4344636487 scopus 로고    scopus 로고
    • Bandula, R.; Vasilesu, M. Rev. Roum. Chim. 1995, 40, 1189-1195; Chem. Abstr. 1996, 125, 114925k.
    • (1996) Chem. Abstr. , vol.125
  • 44
    • 4344633979 scopus 로고    scopus 로고
    • note
    • The formation of ring D was confirmed by the presence of an NOE effect between H-9 and H-12 protons. The chemical shifts of C-9 and C-10 carbons (118.8 and 156.0 ppm, respectively) are also characteristic for an α,β-unsaturated ketone unit.
  • 45
    • 4344593481 scopus 로고    scopus 로고
    • note
    • β proton (3.37 ppm) leads to observation of an NOE at the formyl proton (8.09 ppm), while the tosyl protons gave NOE with H-9 (7.88 ppm).
  • 46
    • 4344646900 scopus 로고    scopus 로고
    • note
    • β protons.
  • 47
    • 4344615084 scopus 로고    scopus 로고
    • note
    • β (3.0 and 3.4 Hz, respectively).
  • 48
    • 4344682305 scopus 로고    scopus 로고
    • note
    • β protons (10.5 Hz).
  • 51
    • 4344582584 scopus 로고    scopus 로고
    • note
    • β protons.
  • 52
    • 4344710976 scopus 로고    scopus 로고
    • note
    • 6 solution 2a experienced a rapid C-8 epimerization and as a result 2b appeared in the isomer mixture.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.