Selenium-Stabilized Carbanions

  • Sylvain Ponthieux
  • Claude Paulmier
Part of the Topics in Current Chemistry book series (TOPCURRCHEM, volume 208)


This chapter presents the main results published during the last ten years, concerning the generation and the reactivity of selenium-stabilized carbanions. Their formation, by α-deprotonation of selenides, selenoxides and selenones or by Se/Li exchange reactions involving selenoacetals, are mentioned. Structural aspects and carbocyclization reactions are also reported.

In a second part, the reactivity of α-phenylselanyl enolates, derived from ketones, esters, lactones and α,β-unsaturated carbonyl compounds, is discussed. Alkylation, aldolisation and Michael reactions are considered as the use of selenium-stabilized carbanions in the natural product synthesis. Others α-functionalyzed species are also presented.

In the last section, the access to a-selanyl vinylmetals is considered. Besides the classical methods involving vinylic selenides and ketene selenoacetals, the hydrometallation (M = Sn, Zr, B) of acetylenic selenides constitutes an efficient method. These species can be considered as vinyl dianion equivalents. Some examples of cross-coupling reactions are presented.


Selenium-stabilized carbanions α-Selanyl enolates Selenides Selenoacetals Alkylation Aldolization Carbocyclization Michael addition 


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7 References

  1. 1.
    Paulmier C (1986) Selenium reagents and intermediates in organic synthesis. Pergamon, OxfordGoogle Scholar
  2. 2.
    Liotta D (1987) Organoselenium chemistry. Wiley, New YorkGoogle Scholar
  3. 3.
    Krief A (1986) Top Curr Chem 135:1Google Scholar
  4. 4.
    Krief A (1987) Synthesis of selenium and tellurium ylides and carbanions: application to organic synthesis. In: Patai S (ed) The chemistry of organic selenium and tellurium compounds, vol 2. John Wiley, New York, chap 17, p 684Google Scholar
  5. 5.
    Reich HJ, Ringer JW (1988) J Org Chem 53:457CrossRefGoogle Scholar
  6. 6.
    Reich HJ (1975) J Org Chem 40:2570CrossRefGoogle Scholar
  7. 7.
    Krief A, Bousbaa J (1997) Tetrahedron Lett 38:6289CrossRefGoogle Scholar
  8. 8.
    Underiner TL, Goering HL (1990) J Org Chem 55:2757CrossRefGoogle Scholar
  9. 9.
    Krief A, Dumont W, Laboureur JL (1988) Tetrahedron Lett 29:3265CrossRefGoogle Scholar
  10. 10.
    Krief A, Dumont W, De Mahieu AF (1988) Tetrahedron Lett 29:3269CrossRefGoogle Scholar
  11. 11.
    Krief A, Dumont W, Clarembeau M, Bernard G, Badaoui E (1989) Tetrahedron 45:2005CrossRefGoogle Scholar
  12. 12.
    Krief A, Dumont W, Clarembeau M, Badaoui E (1989) Tetrahedron 45:2023CrossRefGoogle Scholar
  13. 13.
    Krief A, Nazih A (1995) Tetrahedron Lett 36:8115CrossRefGoogle Scholar
  14. 14.
    Krief A, Evrard G, Badaoui E, De Beys V, Dieden R (1989) Tetrahedron Lett 30:5635CrossRefGoogle Scholar
  15. 15.
    Reich HJ, Bowe MD (1990) J Am Chem Soc 112:8994CrossRefGoogle Scholar
  16. 16.
    Krief A, Defrère L (1996) Tetrahedron Lett 37:8011CrossRefGoogle Scholar
  17. 17.
    Krief A, Defrère L (1996) Tetrahedron Lett 37:8015CrossRefGoogle Scholar
  18. 18.
    Hoffmann RW, Bewersdorf M (1992) Liebigs Ann Chem 643Google Scholar
  19. 19.
    Hoffmann RW, Julius M, Chemla F, Ruhland T, Frenzen G (1994) Tetrahedron 50:6049CrossRefGoogle Scholar
  20. 20.
    Klute W, Dress R, Hoffmann RW (1993) J Chem Soc Perkin Trans 2 1409Google Scholar
  21. 21.
    Hoffmann RW, Klute W, Dress RK, Wenzel A (1995) J Chem Soc Perkin Trans 2 1721Google Scholar
  22. 22.
    Hoffmann RW, Dress RK, Ruhland T, Wenzel A (1995) Chem Ber 128:861CrossRefGoogle Scholar
  23. 23.
    Aggarwal VK (1994) Angew Chem Int Ed Engl 33:175CrossRefGoogle Scholar
  24. 24.
    Klute W, Krüger M, Hoffmann RW (1996) Chem Ber 129:633CrossRefGoogle Scholar
  25. 25.
    Calverley MJ, Strugnell S, Jones G (1993) Tetrahedron 49:739CrossRefGoogle Scholar
  26. 26.
    Krief A, Couty F (1997) Tetrahedron Lett 38:8085CrossRefGoogle Scholar
  27. 27.
    Krief A, Barbeaux P (1991) Tetrahedron Lett 32:417CrossRefGoogle Scholar
  28. 28.
    Krief A, Kenda B, Barbeaux P, Guittet E (1994) Tetrahedron 50:7177CrossRefGoogle Scholar
  29. 29.
    Krief A, Bousbaa J (1997) Tetrahedron Lett 38:6291CrossRefGoogle Scholar
  30. 30.
    Krief A, Barbeaux P, Guittet E (1990) Synlett 509Google Scholar
  31. 31.
    Krief A, Hobe M (1992) Synlett 317Google Scholar
  32. 32.
    Krief A, Hobe M, Dumont W, Badaoui E, Guittet E, Evrard G (1992) Tetrahedron Lett 33:3381CrossRefGoogle Scholar
  33. 33.
    Nicolaou KC, Petasis NA (1984) Selenium in natural products synthesis. CIS, PhiladelphiaGoogle Scholar
  34. 34.
    Kim S, Cheong JH (1997) Synlett 947Google Scholar
  35. 35.
    Kim S, Cheong JH, Yoo J (1998) Synlett 981Google Scholar
  36. 36.
    (a) Kuwahara S, Itoh D, Leal WS, Kodama O (1998) Tetrahedron 54:11421; (b) Kuwahara S, personal communicationCrossRefGoogle Scholar
  37. 37.
    Solomon M, Hoekstra W, Zima G, Liotta D (1988) J Org Chem 53:5058CrossRefGoogle Scholar
  38. 38.
    Ponthieux S, Outurquin F, Paulmier C (1997) Tetrahedron 53:6365CrossRefGoogle Scholar
  39. 39.
    Ponthieux S, Outurquin F, Paulmier C (1998) Tetrahedron Lett 39:4017CrossRefGoogle Scholar
  40. 40.
    Ponthieux S, Outurquin F, Paulmier C (1995) Tetrahedron 51:9569CrossRefGoogle Scholar
  41. 41.
    Ponthieux S, Outurquin F, Paulmier C (1995) Tetrahedron Lett 36:6453CrossRefGoogle Scholar
  42. 42.
    Ponthieux S, Paulmier C, unpublished resultsGoogle Scholar
  43. 43.
    Mathew J (1991) J Chem Soc Perkin Trans 1 2039CrossRefGoogle Scholar
  44. 44.
    Mathew J (1990) J Chem Soc Chem Commun 1264Google Scholar
  45. 45.
    Lebarillier L, Paulmier C, unpublished resultsGoogle Scholar
  46. 46.
    Tsuboi S, Sakamoto J, Sakai T, Utaka M (1989) Chem Lett 1427Google Scholar
  47. 47.
    Fuchigami T, Hayashi T, Konno A (1992) Tetrahedron Lett 33:3161CrossRefGoogle Scholar
  48. 48.
    Hart DJ, Krishnamurthy R (1992) J Org Chem 57:4457CrossRefGoogle Scholar
  49. 49.
    Sugiyama T, Murayama T, Yamashita K (1990) Tetrahedron Lett 31:7343CrossRefGoogle Scholar
  50. 50.
    Franck X, Figadère B, Cavé A (1996) Tetrahedron Lett 37:1593CrossRefGoogle Scholar
  51. 51.
    Kolb HC, Hoffmann HMR (1990) Tetrahedron: Asymmetry 1:237CrossRefGoogle Scholar
  52. 52.
    Toru T, Yamada Y, Ueno T, Maekawa E, Ueno Y (1988) J Am Chem Soc 110:4815CrossRefGoogle Scholar
  53. 53.
    Kusuda S, Ueno Y, Hagiwara T, Toru T (1993) J Chem Soc Perkin Trans 1 1981CrossRefGoogle Scholar
  54. 54.
    Kusuda S, Watanabe Y, Ueno Y, Toru T (1992) J Org Chem 57:3145CrossRefGoogle Scholar
  55. 55.
    Kusuda S, Ueno Y, Toru T (1993) Bull Chem Soc Jpn 66:2720CrossRefGoogle Scholar
  56. 56.
    Kusuda S, Ueno Y, Toru T (1994) Phosphorus Sulfur Silicon Relat Elem 97:63CrossRefGoogle Scholar
  57. 57.
    D’Onofrio F, Parlanti L, Piancatelli G (1996) Synlett 63Google Scholar
  58. 58.
    Bella M, D’Onofrio F, Margarita R, Parlanti L, Piancatelli G, Mangoni A (1997) Tetrahedron Lett 38:7917CrossRefGoogle Scholar
  59. 59.
    Torchiarolo GC, D’Onofrio F, Margarita R, Parlanti L, Piancatelli G, Bella M (1998) Tetrahedron 54:15657CrossRefGoogle Scholar
  60. 60.
    Jahn U, Curran DP (1997) Synlett 565Google Scholar
  61. 61.
    Coutrot P, Grison C, Tabrizi Y (1987) Synthesis 169Google Scholar
  62. 62.
    Simpkins NS (1991) Tetrahedron 47:323CrossRefGoogle Scholar
  63. 63.
    Reich HJ, Holtan RC, Bolm C (1990) J Am Chem Soc 112:5609CrossRefGoogle Scholar
  64. 64.
    Braga AL, Zeni G, De Andrade LH, Silveira CC (1997) Synlett 595Google Scholar
  65. 65.
    Comasseto JV, Menezes PH, Stefani HA, Zeni G, Braga AL (1996) Tetrahedron 52:9687CrossRefGoogle Scholar
  66. 66.
    Braga AL, Reckziegel A, Silveira CC (1994) Synth Commun 28:1165CrossRefGoogle Scholar
  67. 67.
    Chapdelaine MJ, Hulce M (1990) Org React 38:225Google Scholar
  68. 68.
    Lipshutz BH, Sengupta S (1992) Org React 41:135Google Scholar
  69. 69.
    Back TG, Bethell RJ, Parvez M, Wehrli D (1998) J Org Chem 63:7908CrossRefGoogle Scholar
  70. 70.
    Back TG, Wehrli D (1995) Tetrahedron Lett 36:4737Google Scholar
  71. 71.
    Ma Y, Huang X (1997) Synth Commun 27:225CrossRefGoogle Scholar
  72. 72.
    Huang X, Ma Y (1997) Synthesis 417Google Scholar
  73. 73.
    Ma Y, Huang X (1997) Synth Commun 27:3441CrossRefGoogle Scholar
  74. 74.
    Ma Y, Huang X (1998) J Chem Res (S) 312Google Scholar
  75. 75.
    Zhu LS, Huang ZZ, Huang X (1996) J Chem Res (S) 112Google Scholar
  76. 76.
    Huang X, Zhu LS (1996) J Organomet Chem 523:9CrossRefGoogle Scholar
  77. 77.
    Zhu LS, Huang ZZ, Huang X (1996) Tetrahedron 52:9819CrossRefGoogle Scholar
  78. 78.
    Dabdoub MJ, Begnini ML, Guerrero PG Jr (1998) Tetrahedron 54:2371CrossRefGoogle Scholar
  79. 79.
    Sun AM, Huang X (1998) J Chem Res (S) 616Google Scholar
  80. 80.
    Yang, Y, Huang X (1996) J Chem Res (S) 470Google Scholar
  81. 81.
    Yang DY, Huang X (1996) Synth Commun 26:4369CrossRefGoogle Scholar
  82. 82.
    Yang DY, Huang X (1996) Synth Commun 26:4617CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2000

Authors and Affiliations

  • Sylvain Ponthieux
    • 1
  • Claude Paulmier
    • 1
  1. 1.Laboratoire de Synthèse Thio et Sélénoorganique (IRCOF)Université de Rouen, UFR SciencesMont-Saint-Aignan CedexFrance

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