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Volumn 72, Issue 15, 2007, Pages 5592-5597

New access to indolizidine and pyrrolizidine alkaloids from an enantiopure proline: Total syntheses of (-)-lentiginosine and (1R,2R,7aR)- dihydroxypyrrolizidine

Author keywords

[No Author keywords available]

Indexed keywords

DIHYDROXYPROLINE BENZYL ESTER; INDOLIZIDINE; PYRROLIZIDINE;

EID: 34547101686     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo070462w     Document Type: Article
Times cited : (43)

References (66)
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    • For references to the biological activity of indolizidine and pyrrolidine alkaloids, see: a
    • For references to the biological activity of indolizidine and pyrrolidine alkaloids, see: (a) Asano, N.; Nash, R. J.; Molyneux, R. J.; Fleet, G. W. J. Tetrahedron: Asymmetry 2000, 11, 1645-1680.
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    • Asano, N.1    Nash, R.J.2    Molyneux, R.J.3    Fleet, G.W.J.4
  • 4
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    • Brossi, A, Ed, Academic Press: New York, Chapter 3
    • (d) Howard, A. S.; Michael, J. P. In The Alkaloids; Brossi, A., Ed.; Academic Press: New York, 1986; Vol. 28, Chapter 3.
    • (1986) The Alkaloids , vol.28
    • Howard, A.S.1    Michael, J.P.2
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    • and references therein
    • (g) Winkler, D. A.; Holan, G. J. Med. Chem. 1989, 32, 2084-2089 and references therein.
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    • Winkler, D.A.1    Holan, G.2
  • 10
    • 33846914002 scopus 로고    scopus 로고
    • For a recent review of indolizidine and quinolizidine alkaloids, see: a
    • For a recent review of indolizidine and quinolizidine alkaloids, see: (a) Michael, J. P. Nat. Prod. Rep. 2007, 24, 191-222.
    • (2007) Nat. Prod. Rep , vol.24 , pp. 191-222
    • Michael, J.P.1
  • 12
  • 14
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    • For recent examples and leading references to the synthesis of polyhydroxylated indolizidine alkaloids, see: (a) Fujita, T, Nagasawa, H, Uto, Y, Hashimoto, T, Asakawa, Y, Hori, H. Org. Lett. 2004, 6, 827-830
    • For recent examples and leading references to the synthesis of polyhydroxylated indolizidine alkaloids, see: (a) Fujita, T.; Nagasawa, H.; Uto, Y.; Hashimoto, T.; Asakawa, Y.; Hori, H. Org. Lett. 2004, 6, 827-830.
  • 22
    • 0037424028 scopus 로고    scopus 로고
    • For recent examples of and leading references to the synthesis of polyhydroxylated pyrrolizidine alkaloids, see: (a) Ayad, T, Génisson, Y, Baltas, M, Gorrichon, L. Chem. Commun. 2003, 582-583
    • For recent examples of and leading references to the synthesis of polyhydroxylated pyrrolizidine alkaloids, see: (a) Ayad, T.; Génisson, Y.; Baltas, M.; Gorrichon, L. Chem. Commun. 2003, 582-583.
  • 34
    • 0027182313 scopus 로고
    • For leading references to the synthesis of, )-lentiginosine, see: c
    • For leading references to the synthesis of (-)-lentiginosine, see: (c) Yoda, H.; Kitayama, H.; Katagiri, T.; Takabe, K. Tetrahedron: Asymmetry 1993, 4, 1455-1456.
    • (1993) Tetrahedron: Asymmetry , vol.4 , pp. 1455-1456
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  • 38
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    • For leading references to the synthesis of, )-lentiginosine, see: g
    • For leading references to the synthesis of (+)-lentiginosine, see: (g) Ichikawa, Y.; Ito, T.; Nishiyama, T.; Isobe, M. Synlett 2003, 1034-1036.
    • (2003) Synlett , pp. 1034-1036
    • Ichikawa, Y.1    Ito, T.2    Nishiyama, T.3    Isobe, M.4
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    • Alkene 4 is a known compound: Tipson, R. S.; Cohen, A. Carbohydr. Res. 1965, 1, 338-340.
    • (b) Alkene 4 is a known compound: Tipson, R. S.; Cohen, A. Carbohydr. Res. 1965, 1, 338-340.
  • 53
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    • MEM protection was also achieved using CH2Cl2 as the solvent and in a sealed tube. The purity of this reaction was slightly superior, though the yields were lower. The alternate procedure is as follows: To a stirring solution of 10 (280 mg, 0.55 mmol) in a sealed tube in CH2Cl2 (17 mL) at -30°C under N2 were added (i-Pr2)NEt (0.87 mL, 5.0 mmol) and then MEM-Cl (0.38 mL, 3.3 mmol, The reaction mixture was allowed to warm to room temperature, and the system was closed and heated at 80°C for 18 h. The mixture was then cooled, and saturated aqueous NaHCO3 (20 mL) was added. The aqueous layer was extracted with CH2Cl2 (2 x 20 mL, and the combined organic extracts were washed with brine (20 mL, dried (Na2SO 4, and concentrated. Flash chromatography (4:1 hexanes/ EtOAc) gave 12 145 mg, 44, as a clear oil
    • 4), and concentrated. Flash chromatography (4:1 hexanes/ EtOAc) gave 12 (145 mg, 44%) as a clear oil.
  • 65
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    • 4a
    • 4a


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