Effects of Si substitution on the Ei reaction of alkyl sulfoxides

Journal of Organic Chemistry

Volumn 68, Issue 20, 2003, Pages 7871-7879

  McCulla, Ryan D ^a   Jenks, William S ^a  

^a IOWA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ELIMINATION REACTION;

COMPUTATIONAL METHODS; ENTHALPY; REACTION KINETICS; SILICON;

AROMATIC COMPOUNDS;

ALKYL GROUP; SILICON; SULFOXIDE;

ARTICLE; CHEMICAL BOND; ELIMINATION REACTION; ENERGY; ENTHALPY; MATHEMATICAL COMPUTING; MOLECULAR STABILITY; REACTION ANALYSIS; SUBSTITUTION REACTION; THERMODYNAMICS;

EID: 0141542744     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo034690b     Document Type: Article

References (76)

1. Trost, B. M. Chem. Rev. 1978, 78, 363-382.
2. Trost, B. M. Acc. Chem. Res. 1978, 11, 453-461.
3. Moghaddam, F. M.; Ghaffarzadeh, M. Tetrahedron Lett. 1996, 37, 1855-1858.
4. Claes, L.; Francois, J.-P.; Deleuze, M. S. J. Am. Chem. Soc. 2002, 124, 7563-7572.
5. Block, E.; Ahmad, S.; Jain, M. K.; Crecely, R. W.; Apitz-Castro, R.; Cruz, M. R. J. Am. Chem. Soc. 1984, 106, 8295-6.
6. Block, E.; Ahmad, S.; Catalfamo, J. L.; Jain, M. K.; Apitz-Castro, R. J. Am. Chem. Soc. 1986, 108, 7045-55.
7. Oae, S.; Furukawa, N. Tetrahedron 1977, 33, 2359-2367.
8. Back, T. G. Organoselenium Chem. 1999, 7-33.
9. Nishibayashi, Y.; Uemura, S. Top. Curr. Chem. 2000, 208, 201-235.
10. Reich, H. J. Acc. Chem. Res. 1979, 12, 22-30.
11. Cubbage, J. W.; Vos, B. W.; Jenks, W. S. J. Am. Chem. Soc. 2000, 122, 4968-4971.
12. Schmidt-Winkel, P.; Wudl, F. Macromolecules 1998, 31, 2911-2917.
13. Kiran, E.; Gillham, J. K.; Gipstein, E. J. Appl. Polym. Sci. 1977, 21, 1159-1176.
14. Wellisch, E.; Gipstein, E.; Sweeting, O. J. J. Appl. Polym. Sci. 1964, 8, 1623-1631.
15. Cubbage, J. W.; Guo, Y.; McCulla, R. D.; Jenks, W. S. J. Org. Chem. 2001, 66, 8722-8736.
16. Fleming, I.; Goldhill, J.; Perry, D. A. J. Chem. Soc., Perkins Trans. 1 1982, 1563-1569.
17. Fleming, I.; Perry, D. Tetrahedron Lett. 1981, 22, 5095-5096.
18. Nakamura, S.; Watanabe, Y.; Toru, T. J, Org. Chem. 2000, 65, 1758-1766.
19. Nakamura, S.; Kusuda, S.; Kawamura, K.; Toru, T. J. Org. Chem. 2002, 67, 640-647.
20. Jursic, B. S. THEOCHEM 1997, 389, 257-263.
21. Wierschke, S. G.; Chandrasekhar, J.; Jorgensen, W. L. J. Am. Chem. Soc. 1985, 109, 1496-1500.
22. Lambert, J. B.; Wang, G.-t.; Finzel, R.; Teramura, D. J. Am. Chem. Soc. 1987, 109, 7838-7845.
23. Lambert, J. B.; Emblidge, R. W.; Malany, S. J. Am. Chem. Soc. 1993, 115, 1317-1320.
24. Lambert, J. B.; Zhao, Y.; Wu, H. J. Org. Chem. 1999, 64, 2729-2736.
25. Chan, V. Y.; Clark, C. I.; Giordano, J.; Green, A. J.; Karalis, A.; White, J. M. J. Org. Chem. 1996, 61, 5227-5233.
26. Lambert, J. B.; Zhao, Y.; Emblidge, R. W.; Lourdes, S. A.; Liu, X.; So, J.-H.; Chelius, E. C. Acc. Chem. Res. 1999, 32, 183-190.
27. Gabelica, V.; Kresge, A. J. J. Am. Chem. Soc. 1996, 118, 3838-3841.
28. Brook, M. A.; Neuy, A. J. Org. Chem. 1990, 55, 3609-3616.
29. Ochiai, M.; Tada, S.-i.; Sumi, K.; Fujita, E. J. Chem. Soc., Chem. Commun. 1982, 281-282.
30. Ventura, O. N.; Kieninger, M.; Denis, P. A.; Cachau, R. E. Chem. Phys. Lett. 2002, 355, 207-213.
31. Turecek, F. J. Phys. Chem. A 1998, 102, 4703-4713.
32. Martin, J. M. L. J. Chem. Phys. 1998, 108, 2791-2800.
33. Xantheas, S. S.; Dunning, T. H., Jr. J. Phys. Chem. 1993, 97, 6616-27.
34. Bauschlicher, C. W., Jr.; Partridge, H. Chem. Phys. Lett. 1995, 240, 533-540.
35. Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Rassolov, V.; Pople, J. A. J. Chem. Phys. 1998, 109, 7764-7776.
36. Curtiss, L. A.; Raghavachari, K.; Redfern, P. C.; Pople, J. A. J. Chem. Phys. 2000, 112, 7374-7383.
37. Mezey, P. G.; Haas, E.-C. J. Chem. Phys. 1982, 77, 870-876.
38. Hehre, W. 3.1 ed.; Wavefunction, Inc., 18401 Von Karman Ave., Irvine, CA, 1994.
39. Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, N.; Su, S. J.; Windus, T. L.; Dupuis, M.; Montgomery, J. A. J. Comput. Chem. 1993, 14, 1347-1363.
40. Bode, B. M.; Gordon, M. S. J. Mol. Graphics Mod. 1998, 16, 133-138.
41. Typke, V.; Dakkouri, M. J. Mol. Struct. 2001, 599, 177-193.
42. Beagley, B.; Monaghan, J. J.; Hewitt, T. G. J. Mol. Struct. 1971, 401-411.
43. Komornicki, A. J. Am. Chem. Soc. 1984, 106, 3114-3118.
44. Grunenberg, J. Angew. Chem., Int. Ed. 2001, 40, 4027-4029.
45. Gonzales, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, 2154-2161.
46. McCulla, R. D.; Cubbage, J. W.; Jenks, W. S. J. Phys. Org. Chem. 2002, 15, 71-77.
47. The difference is 0 for the products, as they are identical.
48. Fleming, I.; Perry, D. A. Tetrahedron Lett. 1981, 22, 5095-5096.
49. Sunko, D. E.; Szele, I.; Hehre, W. J. J. Am. Chem. Soc. 1977, 99, 5000-5005.
50. Kelly, D. P.; Underwood, G. R.; Barron, P. F. J. Am. Chem. Soc. 1976, 98, 3106-3111.
51. This relationship draws from evidence that the angular dependence of the deuterium kinetic isotop effect and C-H NMR coupling constants follow the same dependence and is similar to arguments made about the strength of twisted π-bonds.
52. This is based on the rate enhancement of the protonation of silylacetylenes.
53. Giambiagi, M.; Giambiagi, M.; Grempel, D. R.; Heymann, C. D. J. Chim. Phys. Phys.-Chim. Biol. 1975, 72, 15-22.
54. Mayer, I. Chem. Phys. Lett. 1983, 97, 270-4.
55. Mayer, I. Chem. Phys. Lett. 1985, 117, 396.
56. In other words, if the bond order in the starting material is 0.90, that in the transition state is 0.60, and that of the products is 0, the fractional progress is 0.33 in that the bond is one-third broken. If a bond is made as a result of the reaction, the fractional progress represents the progress towards forming the bond instead.
57. Wetzel, D. M.; Brauman, J. I. J. Am. Chem. Soc. 1988, 110, 8333-8336.
58. Brinkman, E. A.; Berger, S.; Brauman, J. I. J. Am. Chem. Soc. 1994, 116, 8304-8310.
59. Hopkinson, A. C.; Lien, M. H. J. Org. Chem. 1981, 46, 998-1003.
60. Bank, S.; Sturges, J. S.; Heyer, D.; Bushweller, C. H. J. Am. Chem. Soc. 1980, 102, 3982-4.
61. Bausch, M. J.; Gong, Y. J. Am. Chem. Soc. 1994, 116, 5963-5964.
62. Zhang, X.-m.; Zhang, S.; Bordwell, F. G. J. Am. Chem. Soc. 1995, 117, 602-606.
63. Wetzel, D. M.; Salomon, K. E.; Berger, S.; Brauman, J. I. J. Am. Chem. Soc. 1989, 111, 3835-3841.
64. Giordan, J. C. J. Am. Chem. Soc. 1983, 105, 6544-6546.
65. Streitwieser, A.; Linfeng, X.; Wang, P.; Bachrach, S. M. J. Org. Chem. 1993, 58, 1778-1784.
66. That is, the difference in activation enthalpy between the silyl-and methyl-substituted compounds.
67. Apeloig, Y.; Biton, R.; Abu-Freih, A. J. Am. Chem. Soc. 1993, 115, 2522-2523.
68. Lambert, J. B. Tetrahedron 1990, 46, 2677-2689.
69. Nadler, E. B.; Rappoport, Z.; Arad, D.; Apeloig, Y. J. Am. Chem. Soc. 1987, 109, 7873-7875.
70. Zhang, S.; Bordwell, F. G. J. Org. Chem. 1996, 61, 51-54.
71. Engel, W.; Fleming, I.; Smithers, R. H. J. Chem. Soc., Perkin Trans. 1 1986, 1637.
72. Hypothetically, one could apply the formula for Y by assigning a fractional progress in the transition state and applying it to Δ(ΔH) rather than weighting the isodesmic exchange reactions. However this would violate the principle of microscopic reversibility in that different Y values would be predicted depending on which reaction direction was being considered. This is the case in general when the substituent in question is an "active participant" that changes its bonding dramatically in the reaction rather than a "spectator".
73. It should be pointed out that although at least transiently stable trigonal bipyramidal anionic Si structues are known, we find no evidence for an intermediate in this reaction.
74. Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734-736.
75. Taketsugu, T.; Gordon, M. S. J. Phys. Chem. 1995, 99, 14597-14604.
76. This reaction would obviously never happen because this barrier is much higher than the C-S homolytic bond dissociation energies.