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Selectivity from a kinetic point of view: nonlinear behavior of logarithmic product ratios as a function of the reciprocal temperature

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Abstract

The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.

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References

  1. I. Ojima, Catalytic Asymmetric Synthesis (VCH, Weinheim, 1993).

    Google Scholar 

  2. R. Noyori, Asymmetric Catalysis in Organic Synthesis (Wiley-Interscience, New York, 1994).

    Google Scholar 

  3. C.R. Landis and J. Halpern, J. Am. Chem. Soc. 109 (1987) 1746.

    Article  CAS  Google Scholar 

  4. H. Yamazaki and Y. Wakatsuki, Tetrahedron Lett. (1973) 3383.

  5. H. Bönnemann, R. Brinkmann and H. Schenkluhn, Synthesis (1974) 575.

  6. Y. Wakatsuki and H. Yamazaki, Synthesis (1976) 26.

  7. H. Bönnemann, Angew. Chem. Int. Ed. Engl. 17 (1978) 565.

    Article  Google Scholar 

  8. D.J. Brien, A. Naimann and K.P.C. Vollhardt, J. Chem. Soc., Chem. Commun. (1982) 133.

  9. K.P.C. Vollhardt, Angew. Chem. Int. Ed. Engl. 23 (1984) 539.

    Article  Google Scholar 

  10. H. Bönnemann, Angew. Chem. Int. Ed. Engl. 24 (1985) 248.

    Article  Google Scholar 

  11. C.A. Parnell and K.P.C. Vollhardt, Tetrahedron 41 (1985) 5791.

    Article  CAS  Google Scholar 

  12. A short review on cyclooligomerization reactions with alkynes can be found in B. Cornils and W.A. Herrmann, Applied Homogeneous Catalysis with Organometallic Compounds (VCH, Weinheim, 1996) ch. 3.3.8.

    Google Scholar 

  13. W. Schulz, H. Pracejus and G. Oehme, Tetrahedron Lett. 30 (1989) 1229.

    Article  CAS  Google Scholar 

  14. B. Heller, D. Heller and G. Oehme, J. Mol. Cat. A: Chemical 110 (1996) 211.

    Article  CAS  Google Scholar 

  15. B. Heller, D. Heller, P. Wagler and G. Oehme, submitted for publication.

  16. A description of the experimental procedures for a gas consuming reaction under isobaric conditions with argon/gas mixtures has been reported in D. Heller, J. Holz, S. Borns, A. Spannenberg, R. Kempe, U. Schmidt and A. Börner, Tetrahedron: Asymmetry 8 (1997) 213.

    Article  CAS  Google Scholar 

  17. B. Heller and G. Oehme, J. Chem. Soc., Chem. Commun. (1995) 179.

  18. P. Wagler, B. Heller, J. Ortner, K.-H. Funken and G. Oehme, Chem. Ing. Tech. 68 (1996) 823.

    Article  CAS  Google Scholar 

  19. H.B. Kagan and J.C. Fiaud, in: Topics of Stereochemistry, Vol. 18, eds. E.L. Eliel and S.H. Wilen (Wiley-Interscience, New York, 1988) p. 249.

    Google Scholar 

  20. Y. Sun, C. LeBlond, J. Wang, D.G. Blackmond, J. Laquidara and J.R. Sowa Jr., J. Am. Chem. Soc. 117 (1995) 12647.

    Article  CAS  Google Scholar 

  21. Y. Sun, J. Wang, C. LeBlond, R.N. Landau, J. Laquidara, J.R. Sowa Jr. and D.G. Blackmond, J. Mol. Cat. A: Chemical 115 (1997) 495.

    Article  Google Scholar 

  22. S. Glasstone, K.J. Laidler and H. Eyring, The Theory of Rate Processes (McGraw-Hill, New York, 1941).

    Google Scholar 

  23. H.B. Kagan, Recueil Trav. Chim. Pays-Bas 114 (1995) 203.

    CAS  Google Scholar 

  24. V. Schurig, Enantiomer 1 (1996) 139.

    CAS  Google Scholar 

  25. H. Pracejus, Liebigs Ann. Chem. 634 (1960) 9.

    CAS  Google Scholar 

  26. H. Pracejus, Liebigs Ann. Chem. 634 (1960) 23.

    CAS  Google Scholar 

  27. H. Pracejus, in: Fortschritte der Chemischen Forschung, Vol. 8, eds. E. Heilbronner, U. Hofmann, Kl. Schäfer and G. Wittig (Springer, Berlin, 1967) p. 493.

    Google Scholar 

  28. H. Buschmann, H.-D. Scharf, N. Hoffmann and P. Esser, Angew. Chem. Int. Ed. Engl. 30 (1991) 477.

    Article  Google Scholar 

  29. H. Buschmann, Dissertation, RWTH, Aachen (1993).

  30. H.-D. Scharf and H. Buschmann, Begriffe und Instrumente der Stereochemie (VCH, Weinheim, 1997), in press.

    Google Scholar 

  31. I. Inoue, N. Yamasaki, T. Yokoyama and A. Tai, J. Org. Chem. 57 (1992) 1332.

    Article  CAS  Google Scholar 

  32. T. Göbel and K.B. Sharpless, Angew. Chem. Int. Ed. Engl. 32 (1993) 1329.

    Article  Google Scholar 

  33. J. Muzart, F. Henin, J.-P. Pete and A. M'Boungou-M'Passi, Tetrahedron: Asymmetry 4 (1993) 2531.

    Article  CAS  Google Scholar 

  34. L. Tietze and P. Saling, Chirality 5 (1993) 329.

    Article  CAS  Google Scholar 

  35. I. Toth, I. Guo and B.E. Hanson, Organometallics 12 (1993) 848.

    Article  CAS  Google Scholar 

  36. G.B. Stone, Tetrahedron: Asymmetry 5 (1994) 465.

    Article  CAS  Google Scholar 

  37. I.E. Marko, A. Chesney and D.M. Hollinshead, Tetrahedron: Asymmetry 5 (1994) 569.

    Article  CAS  Google Scholar 

  38. A.K.S. Bhujanga Rao, C. Gundu Rao and B.B. Singh, J. Chem. Soc., Perkin Trans. I (1994) 2399.

  39. Y. Wang and J.A. Gladysz, J. Org. Chem. 60 (1995) 903.

    Article  CAS  Google Scholar 

  40. M.A. Huffmann, N. Yasuda, A.E. DeCamp and E.J.J. Grabowski, J. Org. Chem. 60 (1995) 1590.

    Article  Google Scholar 

  41. G. Cainelli, D. Giacomini and M. Walzl, Angew. Chem. Int. Ed. Engl. 34 (1995) 2150.

    Article  CAS  Google Scholar 

  42. K.A. Parker and M.W. Ledeboer, J. Org. Chem. 61 (1996) 3214.

    Article  CAS  Google Scholar 

  43. G. Cainelli, D. Giacomini, P. Galetti and A. Marini, Angew. Chem. Int. Ed. Engl. 35 (1996) 2849.

    Article  CAS  Google Scholar 

  44. D. Heller, R. Thede and D. Haberland, J. Mol. Cat. A: Chemical 115 (1997) 273.

    Article  CAS  Google Scholar 

  45. H. Buschmann, H.-D. Scharf, N. Hoffmann, M.W. Plath and J. Runsink, J. Am. Chem. Soc. 111 (1989) 5367.

    Article  CAS  Google Scholar 

  46. K.J. Hale and J.H. Ridd, J. Chem. Soc., Chem. Commun. (1995) 357.

  47. K. J. Hale and J. H. Ridd, J. Chem. Soc. Perkin II (1995) 1601.

  48. D. Heller, H. Buschmann and H.-D. Scharf, Angew. Chem. Int. Ed. Engl. 35 (1996) 1852.

    Article  CAS  Google Scholar 

  49. D. Heller, R. Kadyrov, M. Michalik, T. Freier, U. Schmidt and H.W. Krause, Tetrahedron: Asymmetry 7 (1996) 3025.

    Article  CAS  Google Scholar 

  50. H.W. Krause, H. Foken and H. Pracejus, New. J. Chem. 13 (1989) 615.

    CAS  Google Scholar 

  51. H.W. Krause, U. Schmidt, S. Taudien, B. Costisella and M. Michalik, J. Mol. Cat. A: Chemical 104 (1995) 147.

    Article  CAS  Google Scholar 

  52. W.R. Cullen and Y. Sugi, Tetrahedron Lett. (1978) 1635.

  53. R. Selke, React. Kinet. Catal. Lett. 10 (1979) 135.

    Article  CAS  Google Scholar 

  54. R. Jackson and D.J. Thompson, J. Organomet. Chem. 159 (1978) C29.

    Article  CAS  Google Scholar 

  55. R. Selke, J. Organomet. Chem. 370 (1989) 249.

    Article  CAS  Google Scholar 

  56. T.V. RajanBabu, T.A. Ayers and A.L. Casalnuovo, J. Am. Chem. Soc. 116 (1994) 4101.

    Article  CAS  Google Scholar 

  57. S.R. Gilbertson and C.-W.T. Chang, J. Org. Chem. 60 (1995) 6226.

    Article  CAS  Google Scholar 

  58. J. Holz, M. Quirmbach and A. Börner, Synthesis (1997) 983.

  59. H. Brunner and W. Zettelmeier, Handbook of Enantioselective Catalysis with Transition Metal Complexes, Vol. 2 (VCH, Weinheim, 1993).

    Google Scholar 

  60. R. Selke and H. Pracejus, J. Mol. Cat. 37 (1986) 213.

    Article  CAS  Google Scholar 

  61. H.C. Kolb, M.S. VanNieuwenzhe and K.B. Sharpless, Chem. Rev. 94 (1994) 2483.

    Article  CAS  Google Scholar 

  62. D.J. Berrisford, C. Bolm and K.B. Sharpless, Angew. Chem. Int. Ed. Engl. 34 (1995) 1059.

    Article  CAS  Google Scholar 

  63. M. Boudart and G. Djega-Mariadassou, Catal. Let. 29 (1994) 7.

    Article  CAS  Google Scholar 

  64. W. Baumann, S. Mansel, D. Heller and S. Borns, Magn. Res. Chem. 35 (1997) 707.

    Article  Google Scholar 

  65. D. Heller, S. Borns, W. Baumann and R. Selke, Chem. Ber. 129 (1996) 85.

    CAS  Google Scholar 

  66. J.M. Brown, P.A. Chaloner and G.A. Morris, J. Chem. Soc., Chem. Commun. (1983) 664.

  67. J.M. Brown, P.A. Chaloner and G.A. Morris, J. Chem. Soc., Perkin Trans. II (1987) 1583.

  68. H. Bircher, B.R. Bender and W.v. Philipsborn, Magn. Reson. Chem. 31 (1993) 293.

    Article  CAS  Google Scholar 

  69. J.A. Ramsden, T.D.W. Claridge and J.M. Brown, J. Chem. Soc., Chem. Commun. (1995) 2469.

  70. R. Kadyrov, T. Freier, D. Heller, M. Michalik and R. Selke, J. Chem. Soc., Chem. Commun. (1995) 1745.

  71. A. Kless, A. Börner, D. Heller and R. Selke, Organometallics 16 (1997) 2096.

    Article  CAS  Google Scholar 

  72. A.L. Casalnuovo, T.V. RajanBabu, T.A. Ayers and T.H. Warren, J. Am. Chem. Soc. 116 (1994) 9869.

    Article  CAS  Google Scholar 

  73. A. Togni and L.M. Venanzi, Angew. Chem. Int. Ed. Engl. 33 (1994) 497.

    Article  Google Scholar 

  74. G. Li, H.-T. Chang and K.B. Sharpless, Angew. Chem. Int. Ed. Engl. 35 (1996) 451.

    Article  CAS  Google Scholar 

  75. O. Reiser, Angew. Chem. Int. Ed. Engl. 35 (1996) 1308.

    Article  CAS  Google Scholar 

  76. J. Rudolph, P.C. Sennhenn, C.P. Vlaar and K.B. Sharpless, Angew. Chem. Int. Ed. Engl. 35 (1996) 2810.

    Article  CAS  Google Scholar 

  77. G. Li, H.H. Angert and K.B. Sharpless, Angew. Chem. Int. Ed. Engl. 35 (1996) 2813.

    Article  CAS  Google Scholar 

  78. G. Li and K.B. Sharpless, Acta Chemica Scandinavica 50 (1996) 649.

    Article  CAS  Google Scholar 

  79. H.C. Kolb, P.G. Andersson and K.B. Sharpless, J. Am. Chem. Soc. 116 (1994) 1278.

    Article  CAS  Google Scholar 

  80. D.W. Nelson, A. Gypser, P.T. Ho, H.C. Kolb, T. Kondo, H.-L. Kwong, D.V. McGrath, A.E. Rubin, P.-O. Norrby, K.P. Gable and K.B. Sharpless, J. Am. Chem. Soc. 119 (1997) 1840.

    Article  CAS  Google Scholar 

  81. D. Heller and H. Buschmann, submitted for publication.

  82. A. Cornish-Bowden, Principles of Enzyme Kinetics (Butterworth, London, 1976).

    Google Scholar 

  83. D. Heller, H. Buschmann and H. Neumann, J. Mol. Cat. A: Chemical, in press.

  84. E.J. Corey and M.C. Noe, J. Am. Chem. Soc. 118 (1996) 11038.

    Article  CAS  Google Scholar 

  85. S. Dapprich, G. Ujaque, F. Maseras, A. Lledos, D.G. Musaev and K. Morokuma, J. Am. Chem. Soc. 118 (1996) 11660.

    Article  CAS  Google Scholar 

  86. U. Pidun, C. Boehme and G. Frenking, Angew. Chem. Int. Ed. Engl. 35 (1996) 2817.

    Article  CAS  Google Scholar 

  87. M. Torrent, L. Deng, M. Duran, M. Sola and T. Ziegler, Organometallics 16 (1997) 13.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Institut für Organische Katalyseforschung an der Universität Rostock e.V., Buchbinderstraße 5/6, D-18055, Rostock, Germany

    Detlef Heller

  2. Grünenthal GmbH, Aachen, Forschungszentrum, Zieglerstraße 6, D-52078, Aachen, Germany

    Helmut Buschmann

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  1. Detlef Heller
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  2. Helmut Buschmann
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Heller, D., Buschmann, H. Selectivity from a kinetic point of view: nonlinear behavior of logarithmic product ratios as a function of the reciprocal temperature. Topics in Catalysis 5, 159–176 (1998). https://doi.org/10.1023/A:1019185532627

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