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Asymmetric Hydrosilylation of Prochiral Alkenes and Their Derivatives

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Hydrosilylation

Part of the book series: Advances In Silicon Science ((ADSS,volume 1))

Abstract

Asymmetric hydrosilylation of prochiral alkenes followed by Tamao-Fleming oxidation is a convenient method of synthesis of enantioenriched secondary alcohols. In this chapter asymmetric hydrosilylation of unsaturated carbon—carbon bond(s) in various families of reagents such as terminal and internal olefins, cycloolefins, 1,3-dienes, enynes and diynes as well as asymmetric intramolecular hydrosilylation of alkenylsilanes and cyclisation/hydrosilylation of non-conjugated dienes are reviewed. All these transformations proceed efficiently in the presence of palladium and to a minor extent in the presence of rhodium based complexes. Selected processes catalysed by yttrium and lanthanide complexes are also discussed. The chapter ends with brief presentation of some examples of free radical initiated asymmetric hydrosilylation.

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References

  1. K. Tamao, N. Ishida, M. Kumada, J. Org. Chem., 1983, 48, 2120–2122.

    Article  CAS  Google Scholar 

  2. K. Tamao, N. Ishida, T. Tanaka, M. Kumada, Organometallics, 1983, 2, 1694–1696.

    Article  CAS  Google Scholar 

  3. I. Fleming, R. Henning, H. Plaut, J. Chem. Soc., Chem. Commun., 1984, 29–31.

    Google Scholar 

  4. I. Fleming, P.E.J. Sanderson, Tetrahedron Lett., 1987, 28, 4229–4232.

    Article  CAS  Google Scholar 

  5. K. Yamamoto, T. Hayashi, M. Kumada, J. Am. Chem. Soc., 1971, 93, 5301–5302.

    Article  CAS  Google Scholar 

  6. I. Ojima, Z. Li, J. Zhu, Recent advances in the hydrosilylation and related reactions, in: Z. Rappoport, Y. Apeloig (eds) The Chemistry of Organic Silicon Compounds, Wiley, Chichester, 1998, vol. 2, Chapter 29.

    Google Scholar 

  7. M.A. Brook, Silicon in Organic, Organometallic and Polymer Chemistry, Wiley, New York, 2000.

    Google Scholar 

  8. A.K. Roy, Adv. Organomet. Chem., 2008, 55, 1–59.

    Article  CAS  Google Scholar 

  9. B. Marciniec, J. Guliński, H. Maciejewski, Hydrosilylation, in: I.T. Horvath (ed) Encyclopedia of Catalysis, Wiley, New York, 2003, vol. 4, pp. 107–152.

    Google Scholar 

  10. H. Nishiyama, K. Itoh, Asymmetric hydrosilylations and related reactions, in: I. Ojima (ed) Catalytic Asymmetric Synthesis, 2nd Edition, Wiley-VCH, Weinheim, 2000, Chapter 2.

    Google Scholar 

  11. T. Hayashi, Hydrosilylation of carbon—carbon double bonds, in: E.N. Jacobsen, A. Pfaltz, H. Yamamoto (eds) Comprehensive Asymmetric Catalysis, Springer, Berlin, 1999, vol. 1, Chapter 7.

    Google Scholar 

  12. K. Yamamoto, T. Hayashi, Hydrosilylation of olefins, in: M. Beller, C. Bolm (eds) Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals, Wiley-VCH, Weinheim, 2004, vol. 2, Chapter 1.4.1.

    Google Scholar 

  13. T. Hayashi, Acc. Chem. Res., 2000, 33, 354–362.

    Article  CAS  Google Scholar 

  14. T. Hayashi, Catal. Today, 2000, 62, 3–15.

    Article  CAS  Google Scholar 

  15. T. Hayashi, Catal. Surv. Jpn., 1999, 3, 127–135.

    Article  CAS  Google Scholar 

  16. Y. Uozumi, T. Hayashi, J. Am. Chem. Soc., 1991, 113, 9887–9888.

    Article  CAS  Google Scholar 

  17. Y. Uozumi, K. Kitayama, T. Hayashi, K. Yanagi, E. Fukuyo, Bull. Chem. Soc. Jpn., 1995, 68, 713–722.

    Article  CAS  Google Scholar 

  18. T. Hayashi, Y. Uozumi, Pure Appl. Chem., 1992, 64, 1911–1916.

    Article  CAS  Google Scholar 

  19. Y. Uozumi, S.Y. Lee, T. Hayashi, Tetrahedron Lett., 1992, 33, 7185–7188.

    Article  CAS  Google Scholar 

  20. Y. Uozumi, T. Hayashi, Tetrahedron Lett., 1993, 34, 2335–2338.

    Article  CAS  Google Scholar 

  21. B. Heller, A. Gutnov, C. Fischer, H.J. Drexler, A. Spannenberg, D. Redkin, C. Sundermann, B. Sundermann, Chem.Eur. J., 2007, 13, 1117–1128.

    Article  CAS  Google Scholar 

  22. Y. Uozumi, K. Kitayama, T. Hayashi, Tetrahedron: Asymmetry, 1993, 4, 2419–2422.

    Article  CAS  Google Scholar 

  23. K. Kitayama, Y. Uozumi, T. Hayashi, J. Chem. Soc., Chem. Commun., 1995, 1533–1534.

    Google Scholar 

  24. T. Hayashi, S. Niizuma, T. Kamikawa, N. Suzuki, Y. Uozumi, J. Am. Chem. Soc., 1995, 117, 9101–9102.

    Article  CAS  Google Scholar 

  25. G. Bringmann, A. Wuzik, M. Breuning, P. Henschel, K. Peters, E.-M. Peters, Tetrahedron: Asymmetry, 1999, 10, 3025–3031.

    Article  CAS  Google Scholar 

  26. P. Dotta, P. G. A. Kumar, P. S. Pregosin, A. Albinati, S. Rizzato, Organometallics 2004, 23, 2295–2304.

    Article  CAS  Google Scholar 

  27. S. Gladiali, S. Pulacchini, D. Fabbri, M. Manassero, M. Sansoni, Tetrahedron: Asymmetry, 1998, 9, 391–395.

    Article  CAS  Google Scholar 

  28. S. Yasuike, S. Kawara, S. Okajima, H. Seki, K. Yamaguchi, J. Kurita, Tetrahedron Lett.,2004, 45, 9135–9138.

    Article  CAS  Google Scholar 

  29. S. Gladiali, S. Medici, G. Pirri, S. Pulacchini, D. Fabbri, Can. J. Chem., 2001, 79, 670–678.

    Article  CAS  Google Scholar 

  30. T. Hayashi, S. Hirate, K. Kitayama, H. Tsuji, A. Torii, Y. Uozumi, J. Org. Chem., 2001, 66, 1441–1449.

    Article  CAS  Google Scholar 

  31. T. Hayashi, S. Hirate, K. Kitayama, H. Tsuji, A. Torii, Y. Uozumi, Chem. Lett., 2000, 1272–1273.

    Google Scholar 

  32. T. Shimada, K. Mukaide, A. Shinohara, J.W. Han, T. Hayashi, J. Am. Chem. Soc., 2002, 124, 1584–1585.

    Article  CAS  Google Scholar 

  33. T. Hayashi, K. Tamao, Y. Katsuro, I. Nakae, M. Kumada, Tetrahedron Lett., 1980, 21, 1871–1674.

    Article  CAS  Google Scholar 

  34. G. Pioda, A. Togni, Tetrahedron: Asymmetry, 1998, 9, 3903–3910.

    Article  CAS  Google Scholar 

  35. A. Magistrato, T.K. Woo, A. Togni, U. Rothlisberger, Organometallics, 2004, 23, 3218–3227.

    Article  CAS  Google Scholar 

  36. A. Magistrato, A. Togni, U. Rothlisberger, Organometallics, 2006, 25, 1151–1157.

    Article  CAS  Google Scholar 

  37. H.L. Pedersen, M. Johannsen, Chem. Commun., 1999, 2517–2518.

    Google Scholar 

  38. H.L. Pedersen, M. Johannsen, J. Org. Chem., 2002, 67, 7982–7994.

    Article  CAS  Google Scholar 

  39. I. Weber, G.B. Jones, Tetrahedron Lett., 2001, 42, 6983–6986.

    Article  CAS  Google Scholar 

  40. S.E. Gibson, J.T. Rendell, M. Rudd, Synthesis, 2006, 3631–3638.

    Google Scholar 

  41. J.F. Jensen, B.Y. Svendsen, T.V. la Cour, H.L. Pedersen, M. Johannsen, J. Am. Chem. Soc., 2002, 124, 4558–4559.

    Article  CAS  Google Scholar 

  42. X.X. Guo, J.H. Xie, G.H. Hou, W.J. Shi, L.X. Wang, Q.L. Zhou, Tetrahedron: Asymmetry, 2004, 15, 2231–2234.

    Article  CAS  Google Scholar 

  43. M. Tamura, H. Fujihara, J. Am. Chem. Soc., 2003, 125, 15742–15743.

    Article  CAS  Google Scholar 

  44. Y. Uozumi, H. Tsuji, T. Hayashi, J. Org. Chem., 1998, 63, 6137–6140.

    Article  CAS  Google Scholar 

  45. A. Marinetti, Tetrahedron Lett., 1994, 35, 5861–5864.

    Article  CAS  Google Scholar 

  46. A. Marinetti, L. Ricard, Organometallics, 1994, 13, 3956–3962.

    Article  CAS  Google Scholar 

  47. M. Oestreich, S. Rendler, Angew. Chem. Int. Ed., 2005, 44, 1661–1664.

    Article  CAS  Google Scholar 

  48. S. Rendler, M. Oestreich, C.P. Butts, G.C. Lloyd-Jones, J. Am. Chem. Soc., 2007, 129, 502–503.

    Article  CAS  Google Scholar 

  49. Oestreich, M. Chem. Eur. J., 2006, 12, 30–37.

    Article  CAS  Google Scholar 

  50. M. Oestreich, Synlett, 2007, 1629–1643.

    Google Scholar 

  51. T. Hayashi, K. Kabeta, T. Yamamoto, K. Tamao, M. Kumada, Tetrahedron Lett., 1983, 24, 5661–5664.

    Article  CAS  Google Scholar 

  52. T. Hayashi, Y. Matsumoto, I. Morikawa, Y. Ito, Tetrahedron: Asymmetry, 1990, 1, 151–154.

    Article  CAS  Google Scholar 

  53. H. Ohmura, H. Matsuhashi, M. Tanaka, M. Kuroboshi, T. Hiyama, Y. Hatanaka, K. Goda, J. Organomet. Chem., 1995, 499, 167–171.

    Article  CAS  Google Scholar 

  54. J.W. Han, N. Tokunaga, T. Hayashi, Helv. Chim. Acta, 2002, 85, 3848–3854.

    Article  CAS  Google Scholar 

  55. T. Hayashi, S. Hengrasmee, Y. Matsumoto, Chem. Lett., 1990, 1377–1380.

    Google Scholar 

  56. T. Okada, T. Morimoto, K. Achiwa, Chem. Lett., 1990, 999–1002.

    Google Scholar 

  57. S. Sakuraba, T. Okada, T. Morimoto, K. Achiwa, Chem. Pharm. Bull., 1995, 43, 927–934.

    CAS  Google Scholar 

  58. M. Gustafsson, K.E. Bergqvist, T. Frejd, J. Chem. Soc., Perkin Trans. 1, 2001, 1452–1457.

    Article  Google Scholar 

  59. J.M. Blackwell, K.L. Foster, V.H. Beck, W.E. Piers, J. Org. Chem., 1999, 64, 4887–4892.

    Article  CAS  Google Scholar 

  60. Y. Hatanaka, K. Goda, F. Yamashita, T. Hiyama, Tetrahedron Lett., 1994, 35, 7981–7982.

    CAS  Google Scholar 

  61. K. Kitayama, H. Tsuji, Y. Uozumi, T. Hayashi, Tetrahedron Lett., 1996, 37, 4169–4172.

    Article  CAS  Google Scholar 

  62. T. Hayashi, J.W. Han, A. Takeda, J. Tang, K. Nohmi, K. Mukaide, H. Tsuji, Y. Uozumi, Adv. Synth. Catal., 2001, 343, 279–285.

    Article  CAS  Google Scholar 

  63. S. Kobayashi, K. Nishio, J. Org. Chem., 1994, 59, 6620–6628.

    Article  CAS  Google Scholar 

  64. J.W. Han, T. Hayashi, Tetrahedron: Asymmetry, 2002, 13, 325–331.

    Article  CAS  Google Scholar 

  65. T. Hayashi, M. Ishigedani, J. Am. Chem. Soc., 2000, 122, 976–977.

    Article  CAS  Google Scholar 

  66. J.W. Han, N. Tokunaga, T. Hayashi, J. Am. Chem. Soc., 2001, 123, 12915–12916.

    Article  CAS  Google Scholar 

  67. M. Ogasawara, A. Ito, K. Yoshida, T. Hayashi, Organometallics, 2006, 25, 2715–2718.

    Article  CAS  Google Scholar 

  68. R.A. Widenhoefer, M.A. DeCarli, J. Am. Chem. Soc., 1998, 120, 3805–3806.

    Article  CAS  Google Scholar 

  69. N.S. Perch, R.A. Widenhoefer, J. Am. Chem. Soc., 1999, 121, 6960–6961.

    Article  CAS  Google Scholar 

  70. N.S. Perch, T. Pei, R.A. Widenhoefer, J. Org. Chem., 2000, 65, 3836–3845.

    Article  CAS  Google Scholar 

  71. T. Pei, R.A. Widenhoefer, Tetrahedron Lett., 2000, 41, 7597–7600.

    Article  CAS  Google Scholar 

  72. T. Pei, R.A. Widenhoefer, J. Org. Chem., 2001, 66, 7639–7645.

    Article  CAS  Google Scholar 

  73. T. Pei, R.A. Widenhoefer, Org. Lett., 2000, 2, 1469–1471.

    Article  CAS  Google Scholar 

  74. R.A. Windenhoefer, Acc. Chem. Res., 2002, 35, 905–913.

    Article  Google Scholar 

  75. Y. Tsuchiya, H. Uchimura, K. Kobayashi, H. Nishiyama, Synlett, 2004, 2099–2102.

    Google Scholar 

  76. H. Chakrapani, C. Liu, R.A. Widenhoefer, Org. Lett., 2003, 5, 157–159.

    Article  CAS  Google Scholar 

  77. B.M. Fan, J.H. Xie, S. Li, L.X. Wang, Q.L. Zhou, Angew. Chem. Int. Ed., 2007, 46, 1275–1277.

    Article  CAS  Google Scholar 

  78. A. Tillack, D. Michalik, C. Koy, M. Michalik, Tetrahedron Lett., 1999, 40, 6567–6568.

    Article  CAS  Google Scholar 

  79. A. Tillack, C. Koy, D. Michalik, C. Fischer, J. Organomet. Chem., 2000, 603, 116–121.

    Article  CAS  Google Scholar 

  80. K. Tamao, T. Tohma, N. Inui, O. Nakayama, Y. Ito, Tetrahedron Lett., 1990, 31, 7333–7336.

    Article  CAS  Google Scholar 

  81. S.H. Bergens, P. Noheda, J. Whelan, B. Bosnich, J. Am. Chem. Soc., 1992, 114, 2121–2128.

    Article  CAS  Google Scholar 

  82. R.W. Barnhart, X. Wang, P. Noheda, S.H. Bergens, J. Whelan, B. Bosnich, Tetrahedron, 1994, 50, 4335–4346.

    Article  CAS  Google Scholar 

  83. X. Wang, B. Bosnich, Organometallics, 1994, 13, 4131–4133.

    Article  CAS  Google Scholar 

  84. S.H. Bergens, P. Noheda, J. Whelan, B. Bosnich, J. Am. Chem. Soc., 1992, 114, 2128–2135.

    Article  CAS  Google Scholar 

  85. B. Bosnich, Acc. Chem. Res., 1998, 31, 667–674.

    Article  CAS  Google Scholar 

  86. K. Tamao, K. Nakamura, H. Ishii, S. Yamaguchi, M. Shiro, J. Am. Chem. Soc., 1996, 118, 12469–12470.

    Article  CAS  Google Scholar 

  87. T.I. Gountchev, T.D. Tilley, Organometallics, 1999, 18, 5661–5667.

    Article  CAS  Google Scholar 

  88. A.R. Muci, J.E. Bercaw, Tetrahedron Lett., 2000, 41, 7609–7612.

    Article  CAS  Google Scholar 

  89. P-F. Fu, L. Brard, Y. Li, and T. J. Marks, J. Am. Chem. Soc., 1995, 117, 7157–7168.

    Article  CAS  Google Scholar 

  90. F. Buch, J. Brettar, S. Harder, Angew. Chem. Int. Ed., 2006, 45, 2741–2745.

    Article  CAS  Google Scholar 

  91. F. Buch, S. Harder, Zeitschrift fur Naturforschung, 2008, 63b, 169–177.

    Google Scholar 

  92. M. B. Haque, B.P. Roberts, Tetrahedron Lett., 1996, 37, 9123–9126.

    Article  CAS  Google Scholar 

  93. M. B. Haque, B.P. Roberts, D.A. Tocher, J. Chem. Soc., Perkin Trans. 1, 1998, 2881–2889.

    Article  Google Scholar 

  94. Y. Cai, B.P. Roberts, D.A. Tocher, J. Chem. Soc., Perkin Trans. 1, 2002, 1376–1386.

    Article  Google Scholar 

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(2009). Asymmetric Hydrosilylation of Prochiral Alkenes and Their Derivatives. In: Marciniec, B. (eds) Hydrosilylation. Advances In Silicon Science, vol 1. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8172-9_4

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