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Anodic Oxydation of Heterocycles: Alkaloids Synthesis

  • Corinne Bacque-Vanucci
  • Catherine Celimene
  • Marc David
  • Hamid Dhimane
  • Gérard Lhommet
Conference paper

Abstract

The reductive amination of appropriate ketopyrrolidines leading to 3,5-dialkylindolizidines usually gives stereoselectively the indolizidine with a cis relative stereochemistry on the piperidine moiety. We report herein unexpected results concerning the effect of the nature of the C3 subsiituent on this stereoselectivity.

Keywords

Acetyl Chloride Reductive Amination Ester Moiety Chiral Building Block Carbomethoxy Group 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References and notes

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    Tokuyama, T.; Nishimori, N.; Karle, I. L.; Edwards, M. W.; Daly J. W. Tetrahedron 1986, 42, 3453.CrossRefGoogle Scholar
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    Fleurant, A.; Célérier, J. P.; Lhommet, G. Tetrahedron: Asymmetry 1993, 4, 1429.CrossRefGoogle Scholar
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    Machinaga, N.; Kibayashi, C. J. Org. Chem. 1992, 57, 5178. Momose, T; Toyooka, N.; Seki, S.; Hirai, Y. Chem. Pharm. Bull. 1990, 38, 2072.CrossRefGoogle Scholar
  5. 5.
    Célimène, C.; Dhimane, H.; LeBail, M.; Lhommet, G. Tetrahedron Lett. 1994, 35,6105.Trans and cis isomers of 1 were not separable by chromatography.Google Scholar
  6. 6.
    Reduction of 1 was carried out by using NaBH4/CaCl2 system in THE/EtOH (1/1). At this stage the pure trans alcohol 2 was isolated in 67% yield. Acetate 3 was prepared from 2 using acetyl chloride in pyridine (92% yield).Google Scholar
  7. 7.
    Epimers 6 were isolated by column chromatography (Si02, Et20/Pentane, 3/1).Google Scholar
  8. 8.
    The key intermediate 1 could not be separated from its cis isomer (4%) and therefore 5 was used as a trans/cis (96/4) mixture.Google Scholar
  9. 9.
    Product 7b was purified by column chromatography (Si02, Et20/Pentane, 3/1)Google Scholar
  10. 10.
    The two others stereomers were present in too low concentration to be isolated.Google Scholar
  11. 11.
    The ester moiety reduction was performed at -78°C using LiAIH4 in THF.Google Scholar
  12. 12.
    This acetate was obtained by refluxing 9 in THF in the presence of Ac20 (1.1 equiv.) and Et3N (4 equiv.). Otherwise Ac20/Pyridine or Ac20/DCC/DMAP left 9 unchanged. The use of AcCI instead of Ac20 gave a complex mixture.Google Scholar

Copyright information

© Springer Japan 1998

Authors and Affiliations

  • Corinne Bacque-Vanucci
    • 1
  • Catherine Celimene
    • 1
  • Marc David
    • 1
  • Hamid Dhimane
    • 1
  • Gérard Lhommet
    • 1
  1. 1.Laboratoire de Chimie des HétérocyclesUniversité P.& M. CurieParisFrance

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