Download PDF
Synthesis 2009(22): 3797-3802  
DOI: 10.1055/s-0029-1217026
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Straightforward Synthesis of (S)-Anabasine via the Catalytic, Enantio­selective Vinylogous Mukaiyama-Mannich Reaction

David S. Giera, Marcel Sickert, Christoph Schneider*
Institut für Organische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, Germany
Fax: +49(341)9736599; e-Mail: schneider@chemie.uni-leipzig.de;
Further Information

Publication History

Received 19 May 2009
Publication Date:
23 September 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

The tobacco alkaloid (S)-anabasine was synthesized by a straightforward 4-step sequence with the catalytic enantioselective vinylogous Mannich reaction as a key step. Only 3 mol% of a structurally optimized chiral BINOL-based phosphoric acid was employed to control the absolute configuration of the natural product.

Key words

anabasine - piperidine - alkaloids - vinylogous Mannich reaction - Brønsted acid catalysis

    References

  • 1 Strunz GM. Findlay JA. In The Alkaloids   Vol. 26:  Brossi A. Academic Press; New York: 1985.  p.89 
    Google Scholar
  • 2a Pfrengle W. Kunz H. J. Org. Chem.  1989,  54:  4261 
    Google Scholar
  • 2b Pfrengle W. Kunz H. Angew. Chem., Int. Ed. Engl.  1989,  28:  1067 ; Angew. Chem. 1989, 101, 1041
    Google Scholar
  • 2c Hattori K. Yamamoto H. J. Org. Chem.  1992,  57:  3264 
    Google Scholar
  • 2d Hattori K. Yamamoto H. Tetrahedron  1993,  49:  1749 
    Google Scholar
  • 2e Felpin F.-X. Vo-Thanh G. Robins RJ. Villieras J. Lebreton J. Synlett  2000,  1646 
    Google Scholar
  • 2f Felpin F.-X. Girand S. Vo-Thanh G. Robins RJ. Villieras J. Lebreton J. J. Org. Chem  2001,  66:  6305 
    Google Scholar
  • 2g Andres JM. Herraiz-Sierra I. Pedrosa R. Perez-Encabo A. Eur. J. Org. Chem.  2000,  1719 
    Google Scholar
  • 2h Barco A. Benetti S. De Risi C. Marchetti P. Pollini GP. Zanirato V. Eur. J. Org. Chem.  2001,  975 
    Google Scholar
  • 2i Amat M. Canto M. Llor N. Bosch J. Chem. Commun.  2002,  526 
    Google Scholar
  • 2j Jurčík V. Arai K. Salter MM. Yamashita Y. Kobayashi S. Adv. Synth. Catal.  2008,  350:  647 
    Google Scholar
  • 2k Spangenberg T. Breit B. Mann A. Org. Lett.  2009,  11:  261 
    Google Scholar
  • 3a Sickert M. Schneider C. Angew. Chem. Int. Ed.  2008,  47:  3631 ; Angew. Chem. 2008, 120, 3687
    Google Scholar
  • 3b Giera DS. Sickert M. Schneider C. Org. Lett.  2008,  10:  4259 
    Google Scholar
  • For reviews on the vinylogous Mannich reaction, see:
  • 4a Martin SF. Acc. Chem. Res.  2002,  35:  895 
    Google Scholar
  • 4b Bur SK. Martin SF. Tetrahedron  2001,  57:  3221 
    Google Scholar
  • 5 Review: Akiyama T. Chem. Rev.  2007,  107:  5744 ; and references cited therein
    CrossrefPubMedGoogle Scholar
  • 6 Review: Terada M. Chem. Commun.  2008,  4097 ; and references cited therein
    CrossrefGoogle Scholar
  • 7 Gonzalez AS. Arrayas RG. Rivero MR. Carretero JC. Org. Lett.  2008,  10:  4335 
    CrossrefGoogle Scholar
  • 8a Martin SF. Lopez OD. Tetrahedron Lett.  1999,  40:  8949 
    Google Scholar
  • 8b Carswell EL. Snapper ML. Hoveyda AH. Angew. Chem. Int. Ed.  2006,  45:  7230 ; Angew. Chem. 2006, 118, 7388
    Google Scholar
  • 8c Akiyama T. Honma Y. Itoh J. Fuchibe K. Adv. Synth. Catal.  2008,  350:  399 
    Google Scholar
  • 8d For a direct vinylogous Mannich reaction of γ-butenolides, see: Yamaguchi A. Matsunaga S. Shibasaki M. Org. Lett.  2008,  10:  2319 
    Google Scholar
  • 9a Liu TY. Cui HL. Long J. Li BJ. Wu Y. Ding LS. Chen YC. J. Am. Chem. Soc.  2007,  129:  1878 
    Google Scholar
  • 9b Niess B. Jørgensen KA. Chem. Commun.  2007,  1620 
    Google Scholar
  • 10 Review: Adair G. Mukherjee S. List B. Aldrichimica Acta  2008,  41:  31 
    Google Scholar
  • 11 Baker BA. Bošković V. Lipshutz BH. Org. Lett.  2008,  10:  289 
    CrossrefGoogle Scholar
  • 12a Wang M. Yang X.-F. Li C.-J. Eur. J. Org. Chem.  2003,  998 
    Google Scholar
  • 12b Neuvonen H. Neuvonen K. Fülöp F. J. Org. Chem.  2006,  71:  3141 
    Google Scholar
  • 13a Denmark SE. Heemstra JRJr. J. Org. Chem.  2007,  72:  5668 
    Google Scholar
  • 13b Denmark SE. Beutner GL. J. Am. Chem. Soc.  2003,  125:  7800 
    Google Scholar
  • 14a Akiyama T. Itoh J. Yokota K. Fuchibe K. Angew. Chem. Int. Ed.  2004,  43:  1566 ; Angew. Chem. 2004, 116, 1592
    Google Scholar
  • 14b Akiyama T. inventors; PCT Int. Appl. WO  200409675.  ; Chem. Abstr. 2004, 11, 11
  • 15 Maruoka K. Itoh T. Araki Y. Shirasaka T. Yamamoto H. Bull. Chem. Soc. Jpn.  1988,  61:  2975 
    CrossrefGoogle Scholar
  • 16 Storer RI. Carrera DE. Ni Y. MacMillan DWC. J. Am. Chem. Soc.  2006,  128:  84 
    CrossrefGoogle Scholar