Electron-donating and -accepting strength of enoxysilanes and allylsilanes in the reaction with aldehydes

Journal of the American Chemical Society

Volumn 119, Issue 23, 1997, Pages 5366-5372

  Omoto, Kiyoyuki ^a   Fujimoto, Hiroshi ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; ENOXYSILANE; SILICON; UNCLASSIFIED DRUG;

ARTICLE; BINDING KINETICS; CHEMICAL BINDING; ELECTRON TRANSPORT; ION EXCHANGE; MATHEMATICAL COMPUTING; QUANTITATIVE DIAGNOSIS; REACTION ANALYSIS;

EID: 0030742969     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja963677o     Document Type: Article

References (61)

1. Mukaiyama, T.; Banno, K.; Narasaka, K. J. Am. Chem. Soc. 1974, 96, 7503.
2. (a) Kobayashi, S.; Uchiro, H.; Fujishita, Y.; Shiina, I.; Mukaiyama, T. J. Am. Chem. Soc. 1991, 113, 4247.
3. (b) Furuta, K.; Maruyama, T.; Yamamoto, H. J. Am. Chem. Soc. 1991, 113, 1041.
4. (c) Kiyooka, S.; Kaneko, Y.; Komura, M.; Matsuno, H.; Nakano, M. J. Org. Chem. 1991, 56, 2276.
5. (d) Parmee, E. R.; Tempkin, O.; Masamune, S.; Abiko, A. J. Am. Chem. Soc. 1991, 113, 9365.
6. (e) Narasaka, K. Synthesis 1991, 1.
7. Denmark, S. E.; Griedel, B. D.; Coe, D. M.; Schnute, M. E. J. Am. Chem. Soc. 1994, 116, 7026.
8. Denmark, S. E.; Jacobs, R. T.; Dai-Ho, G.; Wilson, S. Organometallics 1990, 9, 3015.
9. Jacobsen, E. N.; Markó, I.; Mungall, W. S.; Schröder, G.; Sharpless, K. B. J. Am. Chem. Soc. 1988, 110, 1968.
10. (a) Myers, A. G.; Widdowson, K. L. J. Am. Chem. Soc. 1990, 112, 9672.
11. (b) Myers, A. G.; Widdowson, K. L.; Kukkola, P. J. J. Am. Chem. Soc. 1992, 114, 2765.
12. (c) Myers, A. G.; Kephart, S. E.; Chen, H. J. Am. Chem. Soc. 1992, 114, 7922.
13. Matsumoto, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1994, 59, 7152.
14. Omoto, K.; Sawada, Y.; Fujimoto, H. J. Am. Chem. Soc. 1996, 118, 1750.
15. Chuit, C.; Corriu, R. J. P.; Reye, C.; Young, J. C. Chem. Rev. 1993, 93, 1371.
16. Corriu, R. J. P.; Guérin, C. J. Organomet. Chem. 1980, 195, 261.
17. Holmes, R. R. Chem. Rev. 1990, 90, 17.
18. Masamune, S.; Choy, W.; Peterson, J. S.; Siat, L. R. Angew. Chem., Int. Ed. Engl. 1985, 24, 1.
19. Maruoka, K.; Hashimoto, S.; Kitagawa, Y.; Yamamoto, H.; Nozaki, H. J. Am. Chem. Soc. 1977, 99, 7705.
20. Heathcock, C. H. Science 1981, 214, 395.
21. Evans, D. A.; McGee, L. R. Tetrahedron Lett. 1980, 21, 3975.
22. Fellmann, P.; Dubois, J. E. Tetrahedron 1978, 34, 1349.
23. Nakamura, E.; Kuwajima, I. Tetrahedron Lett. 1983, 32, 3343.
24. Fujimoto, H.; Satoh, S. J. Phys. Chem. 1994, 98, 1436.
25. (a) Gaussian 92: Frish, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Shlegel, H. B.; Robb, M. A.; Replogle, E. S.; Gomberts, R.; Anders, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A., Gaussian, Inc., Pittsburgh, PA, 1992.
26. (b) Pople, J. A.; Schlegel, H. B.; Krishnan, R.; Defrees, D. J.; Binkley, J. S.; Frisch, M. J., Whiteside, R. A.; Hout, R. F.; Hehre, W. J. Int. J. Quantum Chem. 1981, 15, 269.
27. Møller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618.
28. Ugi, I.; Marquarding, D.; Klusacek, H.; Gillespie, P. Acc. Chem. Res. 1971, 4, 288.
29. Gordon, M. S.; Windus, T. L.; Burgraff, L. W.; Davis, L. P. J. Am. Chem. Soc. 1990, 112, 7167.
30. (a) Fujimoto, H.; Koga, N.; Fukui, K. J. Am. Chem. Soc. 1981, 103, 7452.
31. (b) Fujimoto, H.; Koga, N.; Hataue, I. J. Phys. Chem. 1984, 88, 3539.
32. (c) Fujimoto, H.; Yamasaki, T.; Mizutani, H.; Koga, N. J. Am. Chem. Soc. 1985, 107, 6157.
33. (d) Fujimoto, H.; Yamasaki, T. J. Am. Chem. Soc. 1986, 108, 578.
34. We have also attempted localization of orbitals by utilizing the Boys algorithm (See: Boys, S. F. In Quantum Science of Atoms, Molecules, and Solids; Löwdin, P.-O., Ed.; Academic Press: New York, 1966). Orbitals localized on the Si-C bonds and the one representing the lone-pair electrons of the carbonyl oxygen have been obtained, but the orbital interactions have not been clarified in the present system. For the applications of the method to pentacoordinated silicon species, see for example: Schmidt, M. W.; Windus, T. L.; Gordon, M. S. J. Am. Chem. Soc. 1995, 117, 7480.
35. We have also attempted localization of orbitals by utilizing the Boys algorithm (See: Boys, S. F. In Quantum Science of Atoms, Molecules, and Solids; Löwdin, P.-O., Ed.; Academic Press: New York, 1966). Orbitals localized on the Si-C bonds and the one representing the lone-pair electrons of the carbonyl oxygen have been obtained, but the orbital interactions have not been clarified in the present system. For the applications of the method to pentacoordinated silicon species, see for example: Schmidt, M. W.; Windus, T. L.; Gordon, M. S. J. Am. Chem. Soc. 1995, 117, 7480.
36. Here, the orbital transformations have been carried out for the occupied canonical MO space of the formaldehyde molecule and the unoccupied canonical MO space of the 1-enoxysilacyclobutane molecule. Some additional orbital pairs that have little contribution to the Si-O bonding are also obtained (see ref 23b).
37. Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833, 1841, 2338, 2343.
38. A correlation was also found between the barrier height calculated at the RHF/6-31G level of theory and the energy expectation value of the enoxysilane orbital. It was 0.22 au in Sa and 0.24 au in 5b.
39. Fujimoto, H.; Arita, N.; Tamao, K. Organometallics 1992, 11, 3035 and references cited therein. As for an orbital analysis with the 6-31G** basis set, see: Fujimoto, H.; Yabuki, T.; Tamao, K.; Fukui, K. J. Mol. Struct.: THEOCHEM 1992, 260, 47.
40. Fujimoto, H.; Arita, N.; Tamao, K. Organometallics 1992, 11, 3035 and references cited therein. As for an orbital analysis with the 6-31G** basis set, see: Fujimoto, H.; Yabuki, T.; Tamao, K.; Fukui, K. J. Mol. Struct.: THEOCHEM 1992, 260, 47.
41. Fujimoto, H.; Mizutani, Y.; Iwase, K. J. Phys. Chem. 1986, 90, 2768.
42. Fukui, K.; Fujimoto, H. Bull. Chem. Soc. Jpn. 1968, 41, 1989.
43. r onto the unoccupied MO subspace.
44. Pauling, L. The Nature of the Chemical Bond; Cornell University Press: Ithaca, NY, 1960.
45. (a) Parr, R. G.; Donnelly, R, A.; Levy, M.; Palke, W. E. J. Chem. Phys. 1978, 68, 3801.
46. (b) Parr, R. G.; Pearson, R. G. J. Am. Chem. Soc. 1983, 105, 7512.
47. (c) Parr, R. G.; Yang, W. Density Functonal Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
48. (d) Parr, R. G.; Zhou, Z. Acc. Chem. Res. 1993, 26, 256.
49. (a) Pearson, R. G. J. Am. Chem. Soc. 1963, 85, 3533.
50. (b) Pearson, R. G. J. Am. Chem. Soc. 1985, 107, 6801.
51. (c) Pearson, R. G. Acc. Chem. Res. 1993, 26, 250.
52. Mulliken, R. S. J. Chem. Phys. 1934, 2, 782.
53. Krapivin, A. M.; Mägi, M.; Svergun, V. I.; Zaharjan, R. Z.; Babich, E. D.; Ushakov, N. V. J. Organomet. Chem. 1980, 190, 9.
54. The acidic hardness term has been calculated to be 1.18 au for 5a and 1.31 au for 5b with the s and p hybrid reference orbital.
55. The Si-O bond has also been calculated to be shorter in 5b with C-Si-C fixed at 70° (1.645 Å) than in 5b with C-Si-C fixed at 100° (1.661 Å) at the 6-31G* level of theory.
56. Boatz, J. A.; Gordon, M. S.; Hilderbrandt, R. L. J. Am. Chem. Soc. 1988, 110, 352.
57. The dominant component is the highest occupied MO in most of the substituted silanes studied here. Projection of the 2pπ AO onto the occupied MO space of ethylene gives rise to the highest occupied π MO.
58. Mayr, H.; Patz, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 938.
59. Klopmann, G. Chemical Reactivity and Reaction Paths; Wiley-Interscience: New York, 1974; pp 55-165.
60. Fujimoto, H.; Inagaki, S.; Fukui, K. J. Am. Chem. Soc. 1976, 98, 2670.
61. Yamamoto, Y.; Asano, N. Chem. Rev. 1993, 93, 2207.