Advertisement

Central European Journal of Chemistry

, Volume 12, Issue 5, pp 537–548 | Cite as

50 years of superbases made from organolithium compounds and heavier alkali metal alkoxides

  • Lubomír Lochmann
  • Miroslav Janata
Review Article

Abstract

A review of reactions of organolithium compounds (RLi) with alkali metal alkoxides is presented. On the one hand, simple lithium alkoxides form adducts with RLi the reactivity of which differs only slightly from that of RLi. On the other hand, after mixing heavier alkali metal alkoxides (R’OM, M = Na, K, Rb, Cs) with RLi, a new system is formed, which has reactivity that dramatically exceeds that of the parent RLi. A metal interchange, according to the equation RLi + R’OM = RM + R’OLi, occurs in this system, giving rise to a superbase. This reaction is frequently used for the preparation of heavier alkali metal organometallic compounds. Similar metal interchange takes place between R’OM and compounds such as lithium amides and lithium enolates of ketones or esters, thus demonstrating the general nature of this procedure. Superbases react easily with many types of organic compounds (substrates), resulting in the formation of a heavier alkali metal derivative of the substrate (metalation). The metalated substrate can react in situ with an electrophile to yield the substituted substrate, a procedure that is frequently used in synthetic and polymer chemistry. An improved mechanism of metal interchange and reaction of superbases with substrates is proposed.

Keywords

Superbases Heavier alkali metal compounds Lithium-heavier alkali metal interchange Metalation 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. [1]
    D. Seyferth, Organometallics 28, 2 (2009)Google Scholar
  2. [2]
    J.D. Smith, Adv. Organomet. Chem. 43, 267 (1999)Google Scholar
  3. [3]
    L. Lochmann, J. Pospíšil, J. Vodňanský, J. Trekoval, D. Lím, Collect. Czech. Chem. Commun. 30, 2187 (1965)Google Scholar
  4. [4]
    M. Marsch, K. Harms, L. Lochmann, G. Boche, Angew. Chem. 102, 334 (1990)Google Scholar
  5. [5]
    L. Lochmann, R. Lukáš, D. Lím, Collect. Czech. Chem. Commun. 37, 569 (1972)Google Scholar
  6. [6]
    T. Narita, T. Tsuruta, J. Organomet. Chem. 30, 289 (1971)Google Scholar
  7. [7]
    N. Nugay, T. Nugay, R. Jerome, P. Teyssie, J. Mol. Catal. A-Chem. 179, 59 (2002)Google Scholar
  8. [8]
    C.G. Screttas, B.R. Steele, Appl. Organomet. Chem. 14, 653 (2000)Google Scholar
  9. [9] (a)
    P. Gros, Y. Fort, Eur. J. Org. Chem. 3375 (2002)Google Scholar
  10. [9] (b)
    P. Gros, Y. Fort, Eur. J. Org. Chem. 4199 (2009)Google Scholar
  11. [10]
    A.A. Morton, F.A. Marsh, R.D. Coombs, A.L. Lyons, S.E. Penner, H.E. Ramsden, V.B. Baker, E.L. Little, R.L. Letsinger, J. Am. Chem. Soc. 72, 3785 (1950)Google Scholar
  12. [11]
    C.F. Wofford, USP 3,294.768, Filled November 14 (1963)Google Scholar
  13. [12]
    H.L. Hsieh, C.F. Wofford, J. Polym. Sci. A1, 7, 449 (1969)Google Scholar
  14. [13]
    C.F. Wofford, H.L. Hsieh, J. Polym. Sci. A1, 7, 461 (1969)Google Scholar
  15. [14]
    L. Lochmann, J. Pospíšil, D. Lím, Czech. Pat. 132.254, Filled December 30 (1964) This metal interchange was also awarded as Czechoslovak Disclosure Nr. 60 (1991)Google Scholar
  16. [15]
    L. Lochmann, J. Pospíšil, D. Lím, Tetrahedron Lett. 257 (1966)Google Scholar
  17. [16]
    L. Lochmann, D. Lím, J. Organomet. Chem. 28, 153 (1971)Google Scholar
  18. [17]
    L. Lochmann, J. Trekoval, Collect. Czech. Chem. Commun. 53, 76 (1988)Google Scholar
  19. [18]
    L. Lochmann, Eur. J. Inorg. Chem. 1115 (2000)Google Scholar
  20. [19]
    M. Schlosser, J. Organomet. Chem. 8, 9 (1967)Google Scholar
  21. [20]
    M. Schlosser, Pure Appl. Chem. 60, 1627 (1988)Google Scholar
  22. [21]
    M. Schlosser, Modern Synthetic Methods 6, 227 (1992)Google Scholar
  23. 022]
    M. Schlosser (Ed.), Organometallics in Synthesis. A Manual, 2nd edition (Wiley Chichester, 2002)Google Scholar
  24. [23]
    M. Schlosser, Angew. Chem., Int. Ed. Engl. 44, 376 (2005)Google Scholar
  25. [24]
    E. Weiss, G. Sauermann, G. Thirase, Chem. Ber. 116, 74 (1983)Google Scholar
  26. [25]
    E. Weiss, S. Corbelin, J.K. Cockcroft, A.N. Fitch, Chem. Ber. 123, 1629 (1990)Google Scholar
  27. [26]
    E. Weiss, G. Sauermann, Chem. Ber. 103, 265 (1970)Google Scholar
  28. [27]
    E. Weiss, H. Köster, Chem. Ber. 110, 717 (1977)Google Scholar
  29. [28]
    E. Weiss, G. Sauermann, J. Organomet. Chem. 21, 1 (1970)Google Scholar
  30. [29]
    G. Thirase, E. Weiss, J. Organomet. Chem. 81, C1 (1974)Google Scholar
  31. [30]
    L. Orzechowski, G. Jansen, S. Harder, Angew. Chem., Int. Ed. Engl. 48, 3825 (2009)Google Scholar
  32. [31]
    M. Niemeyer, P.P. Power, Organometallics 16, 3258 (1997)Google Scholar
  33. [32]
    W.H. Glaze, D.P. Duncan, J. Organomet. Chem. 99, 11 (1975)Google Scholar
  34. [33]
    W. Clegg, B. Conway, A.R. Kennedy, J. Klett, R.E. Mulvey, L. Russo, Eur. J. Inorg. Chem. 721 (2011)Google Scholar
  35. [34]
    W.M. Boeasweldt, P.B. Hitchcock, M.F. Lappert, D-S. Liu, S. Tian, Organometallics 19, 4030 (2000)Google Scholar
  36. [35]
    Ch. Schade, W. Bauer, P.v.R. Schleyer, J. Organomet. Chem. 295, C25 (1985)Google Scholar
  37. [36]
    R. Pi, W. Bauer, B. Brix, Ch. Schade, P.v.R. Schleyer, J. Organomet. Chem. 306, C1 (1986)Google Scholar
  38. [37]
    E. Weiss, Angew. Chem., Int. Ed. Engl. 32, 1501 (1993)Google Scholar
  39. [38]
    Ch. Schade, P.v.R. Schleyer, Adv. Organomet. Chem. 27, 169 (1987)Google Scholar
  40. [39]
    W. Clegg, A.R. Kennedy, J. Klett, R.E. Mulvey, L. Russo, Eur. J. Inorg. Chem. 2989 (2012)Google Scholar
  41. [40]
    L. Lochmann, J. Trekoval, Collect. Czech. Chem. Commun. 51, 1439 (1986)Google Scholar
  42. [41]
    W. Bauer, L. Lochmann, J. Am. Chem. Soc. 114, 7482 (1992)Google Scholar
  43. [42]
    D. Hoffmann, W. Bauer, P.v.R. Schleyer, U. Pieper, D. Stalke, Organometallics 12, 1193 (1993)Google Scholar
  44. [43]
    W.F. Bailley, E.R. Punzalan, J. Am. Chem. Soc. 116, 6577 (1994)Google Scholar
  45. [44]
    Eur. Patent Appl. 41306, C.A. 96, 123007 (1981)Google Scholar
  46. [45]
    F.N. Windlin, O. Hutenloch, Ch. Mehler, PTC Int. Appl. WO 2009127559, A1, 22.10. (2009)Google Scholar
  47. [46]
    L. Lochmann, J. Trekoval, J. Organomet. Chem. 326, 1 (1987)Google Scholar
  48. [47]
    G.T. DeLong, D. Hoffmann, H.D. Nguyen, R.D. Thomas, J. Am. Chem. Soc. 119, 11998 (1997)Google Scholar
  49. [48]
    L. Lochmann, J. Čoupek, D. Lím, Collect. Czech. Chem. Commun. 35, 733 (1970)Google Scholar
  50. [49]
    L. Lochmann, J. Trekoval, J. Organomet. Chem. 179, 123 (1979)Google Scholar
  51. [50]
    K. Gregory, M. Bremer, W. Bauer, P.v.R. Schleyer, N.P. Lorenzen, J. Kopf, E. Weiss, Organometallics 9, 1485 (1990)Google Scholar
  52. [51]
    S.T. Liddle, W. Clegg, Polyhedron 22, 3507 (2003)Google Scholar
  53. [52]
    A.R. Kennedy, J. MacLellan, R.E. Mulvey, A. Robertson, J. Chem. Soc., Dalton Trans. 4112 (2000)Google Scholar
  54. [53]
    P.A.A. Klusener, L. Tip, L. Brandsma, Tetrahedron 47, 2041 (1991)Google Scholar
  55. [54]
    S. Raucher, G.A. Koolpe, J. Organomet. Chem. 43, 3794 (1978)Google Scholar
  56. [55]
    L. Lochmann, R.L. De, J. Trekoval, J. Organomet. Chem. 156, 307 (1978)Google Scholar
  57. [56]
    L. Lochmann, J. Trekoval, J. Organomet. Chem. 99, 329 (1975)Google Scholar
  58. [57]
    V. Halaška, L. Lochmann, Collect. Czech. Chem. Commun. 33, 3245 (1968)Google Scholar
  59. [58]
    H.J. Reich, Chem. Rev.113, 7130 (2013)Google Scholar
  60. [59]
    T.L. Brown, Pure Appl. Chem. 23, 447 (1970)Google Scholar
  61. [60]
    H.L. Hsieh, R.P. Quirck, Ionic Polymerization (M. Decker, Inc., New York, Basel, Hongkong, 1996) 131–154Google Scholar
  62. [61]
    T.F. Bates, M.T. Clarke, R.D. Thomas, J. Am. Chem. Soc. 110, 5109 (1988)Google Scholar
  63. [62]
    J.F. McGarrity, C.A. Ogle, J. Am. Chem. Soc.107, 1805 (1984)Google Scholar
  64. [63]
    V. Halaška, L. Lochmann, Collect. Czech. Chem. Commun. 38, 1780 (1973)Google Scholar
  65. [64]
    G.T. DeLong, D.K. Pannell, M.T. Clarke, R.D. Thomas, J. Am. Chem. Soc. 115, 7013 (1993)Google Scholar
  66. [65]
    K.W. Henderson, P.G. Walther, J. Williard, J. Am. Chem. Soc. 117, 8680 (1995)Google Scholar
  67. [66]
    D. Seebach, Angew. Chem., Int. Ed. Engl. 27, 1624 (1988)Google Scholar
  68. [67]
    T.L. Brown, J.A. Ladd, G.M. Newman, J. Organomet. Chem. 3, 1 (1965)Google Scholar
  69. [68]
    T.L. Brown, Acc. Chem. Res. 1, 23 (1968)Google Scholar
  70. [69]
    S. Harder, A. Streitwieser, Angew. Chem., Int. Ed. Engl. 32, 1066 (1993)Google Scholar
  71. [70]
    D.R. Armstrong, W. Clegg, A.M. Drummond, S.T. Liddle, R.E. Mulvey, J. Am. Chem. Soc. 122, 11117 (2000)Google Scholar
  72. [71]
    P.G. Williard, G.J. MacEvan, J. Am. Chem. Soc. 111, 7671 (1989)Google Scholar
  73. [72]
    S. Harder, M. Lutz, T. Kremer, Organometallics 14, 2133 (1995)Google Scholar
  74. [73]
    R. Holland, J.C. Jeffery, C.A. Russell, J. Chem. Soc., Dalton Trans. 3331 (1999)Google Scholar
  75. [74]
    K.M. Fromm, E.D. Gueneau, Polyhedron 23, 1479 (2004)Google Scholar
  76. [75]
    P.D. Bartlett, C.V. Goebel, W.P. Weber, J. Am. Chem. Soc. 91, 7425 (1969)Google Scholar
  77. [76]
    M. Schlosser, J.H. Choi, S. Takagishi, Tetrahedron 46, 5633 (1990)Google Scholar
  78. [77]
    L. Lochmann, J. Organomet. Chem. 364, 281 (1989)Google Scholar
  79. [78]
    L. Lochmann, J. Organomet. Chem. 376, 1 (1989)Google Scholar
  80. [79]
    M.Y. Darensbourgh, B.Y. Kimura, G.E. Hartwell, T.L. Brown, J. Am. Chem. Soc. 92, 1237 (1970)Google Scholar
  81. [80]
    V.H. Gessner, Ch. Däschlein, C. Strohmann, Chem. Eur. J. 15, 3320 (2009)Google Scholar
  82. [81]
    L. Lochmann, H. Jakubův, L. Brandsma, Collect. Czech. Chem. Commun. 58, 1445 (1993)Google Scholar
  83. [82]
    G. Klopman, J. Am. Chem. Soc. 90, 223 (1968)Google Scholar
  84. [83]
    R.G. Pearson, J. Am. Chem. Soc. 85, 3533 (1963)Google Scholar
  85. [84]
    T. Kremer, S. Harder, M. Junge, P.v.R. Schleyer, Organometallics 15, 585 (1996)Google Scholar
  86. [85]
    G. Ghio, G. Tonachini, P. Venturello, Tetrahedron 52, 7053 (1996)Google Scholar
  87. [86]
    L. Lochmann, Collect. Czech. Chem. Commun. 52, 2710 (1987)Google Scholar
  88. [87]
    D. Bucca, B. Gordon III., Macromolecules 27, 862 (1994)Google Scholar
  89. [88]
    M.S. Hill, P.B. Hitchcock, J. Organomet. Chem. 664, 182 (2002)Google Scholar
  90. [89]
    G. Boche, H. Etzrodt, Tetrahedron Lett. 24, 5477 (1983)Google Scholar
  91. [90]
    U. Pieper, D. Stalke, Organometallics 12, 1201 (1993)Google Scholar
  92. [91]
    D. Wilhelm, W.D. Clark, P.v.R. Schleyer, J.L. Courtneidge, A.G. Davies, J. Organomet. Chem. 273, C1 (1984)Google Scholar
  93. [92]
    D. Hoffmann, W. Bauer, F.N. Hampel, J.R. Nicolaas, J.R. van Eikema Hommes, P.v.R. Schleyer, P. Otto, U. Pieper, D. Stalke, D.S. Wright, R. Snait, J. Am. Chem. Soc. 116, 528 (1994)Google Scholar
  94. [93]
    S.C. Goel, E. Grovenstein Jr., Organometallics 11, 1565 (1992)Google Scholar
  95. [94]
    F.H. Köhler, N. Hertkorn, Chem. Ber. 116, 3274 (1983)Google Scholar
  96. [95]
    L. Lochmann, M. Rodová, J. Trekoval, J. Polym. Sci., Part A: Polym. Chem. 12, 2091 (1974)Google Scholar
  97. [96]
    L. Lochmann, D. Doskočilová, J. Trekoval, Collect. Czech. Chem. Commun. 42, 1355 (1977)Google Scholar
  98. [97]
    R.B. Bates, T.J. Siahaan, K. Suvannachut, J. Organomet. Chem. 55, 1328 (1990)Google Scholar
  99. [98]
    D. Wilhelm, T. Clark, T. Friedl, P.v.R. Schleyer, Chem. Ber. 116, 751 (1983)Google Scholar
  100. [99]
    D. Wilhelm, T. Clark, P.v.R. Schleyer, J. Chem. Soc., Chem. Commun. 211 (1983)Google Scholar
  101. [100]
    D. Wilhelm, T. Clark, P.v.R. Schleyer, J.L. Courtneidge, A.G. Davies, J. Am. Soc. 106, 361 (1984)Google Scholar
  102. [101]
    L. Lochmann, J. Petránek, Tetrahedron Lett. 32, 1483 (1991)Google Scholar
  103. [102]
    H. Andriga, H.D. Verkruijsse, L. Brandsma, L. Lochmann, J. Organomet. Chem. 393, 307 (1990)Google Scholar
  104. [103]
    L. Lochmann, Dissertation D.Sc., Organic Compounds of Alkali Metals in Macromolecular Chemistry (Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Czech Republic, 1997)Google Scholar
  105. [104]
    L. Lochmann, J.M.J. Frechet, Macromolecules 29, 1767 (1996)Google Scholar
  106. [105]
    J.H.K. Steinke, S.A. Haque, J.M.J. Frechet, H.C. Wang, Macromolecules 29, 6081 (1996)Google Scholar
  107. [106]
    J.-M. Marechal, S. Carlotti, L. Shchleglova, A. Deffieux, Polymer 44, 7601 (2003)Google Scholar
  108. [107]
    B.I. Nakhmanovich, I.V. Zolotareva, A.A. Arest-Yakubovich, Macromol. Chem. Phys. 200, 2015 (1999)Google Scholar
  109. [108]
    D.B. Collum, A.J. McNeil, A. Ramirez, Angew. Chem., Int. Ed. Engl. 46, 3002 (2007)Google Scholar
  110. [109]
    M. Schlosser, F. Faigl, L. Franzini, H. Geneste, G. Katsoulos, Z. Guo-fu, Pure and Appl. Chem. 66, 1439 (1994)Google Scholar
  111. [110]
    D.A. Shirley, J.P. Hendrix, J. Organomet. Chem. 11, 217 (1968)Google Scholar
  112. [111]
    D. Wilhelm, T. Clark, J.L. Courtneidge, A.G. Davies, J. Chem. Soc., Chem. Commun. 213 (1983)Google Scholar
  113. [112]
    W.J. Trepka, J.A. Favre, R.J. Sonnenfeld, J. Organomet. Chem. 55, 271 (1973)Google Scholar
  114. [113]
    D.B. Patterson, A.F. Halasa, Macromolecules 24, 4489 (1991)Google Scholar
  115. [114]
    M. Schlosser, S. Strunk, Tetrahedron Lett. 25, 741 (1984)Google Scholar
  116. [115]
    W.E. Paget, K. Smith, M.G. Hutchings, G.E. Martin, J. Chem. Res. 327 (1983)Google Scholar
  117. [116]
    R.V. Basova, Z.F. Didenko, A.R. Gantmacher, S.S. Medvedev, Vysokomol. Soedin., B 14, 272 (1972) (in Russian)Google Scholar
  118. [117]
    A. Deagostino, P.B. Tivola, C. Prandi, P. Venturello, J. Chem. Soc., Perkin Trans. I, 2856 (2001)Google Scholar
  119. [118]
    E. Marzi, J. Gorecka, M. Schlosser, Synthesis 1609 (2004)Google Scholar
  120. [119]
    A. Deagostino, C. Prandi, P. Venturello, Curr. Org. Chem. 7, 821 (2003)Google Scholar
  121. [120]
    E. Marzi, A. Spitaleri, F. Mongin, M. Schlosser, Eur. J. Org. Chem. 2508 (2002)Google Scholar
  122. [121]
    A. Deagostino, A. Migliardi, E.G. Occhiato, C. Prandi, C. Zavattaro, P. Venturello, Tetrahedron 61, 3429 (2005)Google Scholar
  123. [122]
    L. Brandsma, H.D. Verkruijsse, Preparative Polar Organometallic Chemistry (Springer, Berlin, 1987) Vol. 1Google Scholar
  124. [123]
    L. Brandsma, Preparative Polar Organometallic Chemistry (Springer, Berlin, 1990) Vol. 2Google Scholar
  125. [124]
    Ch. Tai, A.F. Halasa, D.P. Tate, J. Polym. Sci., Part A: Polym. Chem. 11, 253 (1973)Google Scholar
  126. [125]
    Ch. Tai, A.F. Halasa, J. Polym. Sci., Part A: Polym. Chem. 14, 573 (1976)Google Scholar
  127. [126]
    A.A. Arest-Yakubovich, G.I. Litvinenko, Prog. Polym. Sci. 21, 335 (1996)Google Scholar
  128. [127]
    A.A. Arest-Yakubovich, I.V. Zolotareva, N.J. Pakuro, E.V. Kristalnyi, B.I. Nakhmanovich, Vysokomol. Soedin., A 38, 418 (1996) (in Russian)Google Scholar
  129. [128]
    B. Gordon III., M. Blumenthal, Polym. Bull. 14, 69 (1985)Google Scholar
  130. [129]
    B. Gordon III., J. Loftus, D. Bucca, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 29, 21 (1988)Google Scholar
  131. [130]
    S. Ying, Macromol. Symp. 85, 251 (1994)Google Scholar
  132. [131]
    F. Yu, W. Chen, Y. Wang, R. Mu, S. Ying, Ta-lien Kung Hsueh Yuan Hsueh Pao 20(Suppl. 1), 43 (1981); C.A. 95: 204521s (1981)Google Scholar
  133. [132]
    S.D. Smith, A. Ashraf, S.J. Clarson, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 35(2), 466 (1994)Google Scholar
  134. [133]
    L. Lochmann, J. Kolařík, D. Doskočilova, S. Vozka, J. Trekoval, J. Polym. Sci., Part A: Polym. Chem. 17, 1727 (1979)Google Scholar
  135. [134]
    P. Vlček, L. Lochmann, Prog. Polym. Sci. 24, 793 (1999)Google Scholar
  136. [135]
    N. Ekizoglou, N. Hadjichristidis, J. Polym. Sci., Part A: Polym. Chem. 39, 1198 (2001)Google Scholar
  137. [136]
    S. Nemes, J. Borbély, J. Borda, T. Kelen, Polym. Bull. 27, 123 (1991)Google Scholar
  138. [137]
    S. Nemes, J.P. Kennedy, J. Macromol. Sci. Chem., A28, 311 (1991)Google Scholar
  139. [138]
    A.F. Halasa, G.B. Mitchell, M. Stayer, D.P. Tate, A.E. Oberster, R.W. Koch, J. Polym. Sci., Part A: Polym. Chem. 14, 497 (1976)Google Scholar
  140. [139]
    M.V. Chirkova, P.V. Pivovarov, E.G. Litvinova, V.S. Khotimskii, Polymer Science, Ser. A48, 489 (2006)Google Scholar
  141. [140]
    L. Lochmann, K. Wooley, P.T. Ivanova, J.M.J. Frechet, J. Am. Chem. Soc. 115, 7043 (1993)Google Scholar
  142. [141]
    S. Nemes, K.L. Peng, L. Wilczek, J.P. Kennedy, Polym. Bull. 24, 187 (1990)Google Scholar
  143. [142]
    M. Janata, L. Lochmann, J. Brus, P. Vlček, Macromolecules 34, 1593 (2001)Google Scholar
  144. [143]
    J.A. Amass, E.W. Duck, J.R. Hawkins, J.M. Locke, Eur. Polym. J. 8, 781 (1972)Google Scholar
  145. [144]
    L. Lochmann, M. Janata, P. Holler, Z. Tuzar, P. Kratochvíl, Macromolecules 29, 8092 (1996)Google Scholar
  146. [145]
    M. Janata, L. Lochmann, J. Brus, P. Holler, Z. Tuzar, P. Kratochvíl, B. Smitt, W. Radke, A.H.E. Müller, Macromolecules 30, 7370 (1997)Google Scholar
  147. [146]
    M. Janata, J. Brus, L. Lochmann, P. Vlček, Macromol. Chem. Phys. 202, 3293 (2001)Google Scholar

Copyright information

© Versita Warsaw and Springer-Verlag Wien 2014

Authors and Affiliations

  1. 1.Institute of Macromolecular Chemistry of Academy of Sciences of the Czech RepublicPrague 6Czech Republic

Personalised recommendations