Orbital unsymmetrization of olefins arising from non-equivalent orbital interactions. σ-π Coupling in bicyclo[2.2.2]octenes

Chemical and Pharmaceutical Bulletin

Volumn 44, Issue 2, 1996, Pages 296-306

  Ohwada, Tomohiko ^a   Uchiyama, Masanobu ^a   Tsuji, Motonori ^a   Okamoto, Iwao ^a   Shudo, Koichi ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

bicyclo 2.2.2 octene; methylenenorbornane; olefin; orbital unsymmetrization; coupling

Indexed keywords

ALKENE; BICYCLO[2.2.2]OCTANE DERIVATIVE;

ARTICLE; CARBOXYLATION; DRUG EFFECT; DRUG STRUCTURE; EPOXIDATION; HYDROXYLATION; NONHUMAN; PROTEIN DNA INTERACTION; REACTION ANALYSIS; STEREOCHEMISTRY; STIMULUS SECRETION COUPLING; STRUCTURE ANALYSIS;

EID: 0029979433     PISSN: 00092363     EISSN: None     Source Type: Journal    
DOI: 10.1248/cpb.44.296     Document Type: Article

References (82)

1. le Noble W. J., Recl. Trav. Chim. Pays-Bas, 111, 199-210 (1992).
2. Cheung C. K., Tseng L. T., Lin M.-H., Srivastava S., le Noble W. J., J. Am. Chem. Soc., 108, 1598-1605 (1986)
3. a) Mehta G., Khan F. A., J. Chem. Soc., Chem. Commun., 1991, 18-19;
4. b) Mehta G., Khan F. A., Gadre S. R., Shirsat R. N., Ganguly B., Chandrasekhar J., Angew. Chem. Int. Ed. Engl., 33, 1390-1392 (1994).
5. Jones G. R., Vogel P., J. Chem. Soc., Chem. Commun., 1993, 769-771.
6. a) Giddings M R., Hudec J., Can. J. Chem., 59, 459-467 (1981);
7. b) Srivastava S., le Noble W. J., J. Am. Chem. Soc., 109, 5874-5875 (1987);
8. c) Chung W.-S., Turro N. J., Srivastava S., Li H., le Noble W. J., J. Am. Chem. Soc., 110, 7882-7883 (1988).
9. Mehta G., Khan F. A., J. Am. Chem. Soc., 112, 6140-6142 (1990); Mehta G., Praveen M., Tetrahedron Lett., 33, 1759-1762 (1992).
10. Mehta G., Khan F. A., J. Am. Chem. Soc., 112, 6140-6142 (1990); Mehta G., Praveen M., Tetrahedron Lett., 33, 1759-1762 (1992).
11. Mehta G , Khan F. A., Tetrahedron Lett., 33, 3065-3068 (1992); Keserü G. M., Kajtár-Peredy M., Náray-Szabó G., Tetrahedron Lett., 35, 9255-9258 (1994).
12. Mehta G , Khan F. A., Tetrahedron Lett., 33, 3065-3068 (1992); Keserü G. M., Kajtár-Peredy M., Náray-Szabó G., Tetrahedron Lett., 35, 9255-9258 (1994).
13. Okada K., Tomita S., Oda M., Bull. Chem. Soc. Jpn., 62, 459-468 (1989); Okada K., Tomita S., Oda M., Tetrahedron Lett., 27, 2645-2648 (1986).
14. Okada K., Tomita S., Oda M., Bull. Chem. Soc. Jpn., 62, 459-468 (1989); Okada K., Tomita S., Oda M., Tetrahedron Lett., 27, 2645-2648 (1986).
15. Mehta G., Khan F. A., Ganguly B., Chandrasekhar J., J. Chem. Soc., Chem. Commun., 1992, 1711-1712.
16. Pudzianowski A. T , Barrish J. C., Spergel S. H., Tetrahedron Lett., 33, 293-296 (1992).
17. a) Wu Y.-D., Tucker J. A., Houk K. N., J Am. Chem. Soc., 113, 5018-5027 (1991);
18. b) Paddon-Row M. N., Wu Y.-D., Houk K. N., J. Am. Chem. Soc., 114, 10638-10639 (1992);
19. c) Williams L., Paddon-Row M. N., J. Chem. Soc., Chem. Commun., 1994, 353-355,
20. d) Kumar V. A., Venkatesan K., Ganguly B., Khan F. A., Mehta G., Tetrahedron Lett., 33, 3069-3072 (1992); Gangly B , Chandrasekhar J., Khan F. A., Mehta G., J. Org. Chem., 58, 1734-1739 (1993).
21. d) Kumar V. A., Venkatesan K., Ganguly B., Khan F. A., Mehta G., Tetrahedron Lett., 33, 3069-3072 (1992); Gangly B , Chandrasekhar J., Khan F. A., Mehta G., J. Org. Chem., 58, 1734-1739 (1993).
22. Cieplak A. S., J. Am. Chem. Soc., 103, 4540-4552 (1981)
23. Klein J., Tetrahedron Lett , 1973, 4307-4310; Klein J., Tetrahedron, 30, 3349-3353 (1974).
24. Klein J., Tetrahedron Lett , 1973, 4307-4310; Klein J., Tetrahedron, 30, 3349-3353 (1974).
25. Frenking G., Köhler K F., Reetz M. T., Angew. Chem. Int. Ed. Engl., 30, 1146-1149 (1991).
26. Houk K. N., Paddon-Row M. N., Rondan N. G., Wu Y.-D., Brown F. K., Spellmeyer D. C., Metz J T., Li Y., Loncharich R. J., Science, 231, 1108-1117 (1986).
27. 7-Isopropylidenebenzonorbornenes: Okada K., Mukai T., J. Am. Chem. Soc , 100, 6509-6510 (1978); Paquette L. A., Hertel L. W., Gleiter R., Böhm M., J. Am. Chem. Soc., 100, 6510-6512 (1978).
28. 7-Isopropylidenebenzonorbornenes: Okada K., Mukai T., J. Am. Chem. Soc , 100, 6509-6510 (1978); Paquette L. A., Hertel L. W., Gleiter R., Böhm M., J. Am. Chem. Soc., 100, 6510-6512 (1978).
29. Bach R. D., Owensby A. L., Gonzalez C., Schlegel H. B., J. Am. Chem. Soc., 113, 2338-2339 (1991).
30. Jorgensen K. A., Hoffmann R., J. Am. Chem. Soc., 108, 1867-1876 (1986); Jorgensen K. A., Tetrahedron Lett., 31, 6417-6420 (1990); Wu Y.-D., Wang Y., Houk K. N., J. Org. Chem., 57, 1362-1369 (1992).
31. Jorgensen K. A., Hoffmann R., J. Am. Chem. Soc., 108, 1867-1876 (1986); Jorgensen K. A., Tetrahedron Lett., 31, 6417-6420 (1990); Wu Y.-D., Wang Y., Houk K. N., J. Org. Chem., 57, 1362-1369 (1992).
32. Jorgensen K. A., Hoffmann R., J. Am. Chem. Soc., 108, 1867-1876 (1986); Jorgensen K. A., Tetrahedron Lett., 31, 6417-6420 (1990); Wu Y.-D., Wang Y., Houk K. N., J. Org. Chem., 57, 1362-1369 (1992).
33. Ohwada T , Shudo K., Chem. Pharm. Bull., 39, 2176-2178 (1991); Ohwada T., J. Am. Chem. Soc., 114, 8818-8827 (1992); Ohwada T., Tetrahedron, 49, 7649 7656 (1993).
34. Ohwada T , Shudo K., Chem. Pharm. Bull., 39, 2176-2178 (1991); Ohwada T., J. Am. Chem. Soc., 114, 8818-8827 (1992); Ohwada T., Tetrahedron, 49, 7649 7656 (1993).
35. Ohwada T , Shudo K., Chem. Pharm. Bull., 39, 2176-2178 (1991); Ohwada T., J. Am. Chem. Soc., 114, 8818-8827 (1992); Ohwada T., Tetrahedron, 49, 7649 7656 (1993).
36. Ohwada T., Okamoto I., Haga N., Shudo K., J. Org. Chem., 59, 3975-3984 (1994).
37. Goldstein M. J., Hoffmann R., J. Am. Chem. Soc., 93, 6193-6204 (1971).
38. Albright T. A., Burdett J. K., Whangbo M-H., "Orbital Interactions in Chemistry," John Wiley & Sons, Inc., New York, 1985; Rauk A., "Orbital Interaction Theory of Organic Chemistry," John Wiley & Sons, Inc., New York, 1994.
39. Albright T. A., Burdett J. K., Whangbo M-H., "Orbital Interactions in Chemistry," John Wiley & Sons, Inc., New York, 1985; Rauk A., "Orbital Interaction Theory of Organic Chemistry," John Wiley & Sons, Inc., New York, 1994.
40. a) Hariharan P. C., Pople J. A., Chem. Phys. Lett., 16, 217-219 (1972);
41. b) Hehre W. J., Radom L., Schleyer P. V. R., Pople J. A., "Ab Initio Molecular Orbital Theory," Wiley and Sons, Inc., New York, 1986.
42. Hoffmann R., Mollere P. D., Heilbronner E., J. Am. Chem. Soc., 95, 4860-4862 (1973).
43. 2 = CN) there is no significant rehybridization of the π orbital of the olefin. Rehybridization model: Inagaki S., Fukui K., Chem. Lett., 1974, 509-514; Inagaki S., Fujimoto H., Fukui K., J. Am. Chem. Soc., 98, 4054-4061 (1976); Ishida M., Beniya Y., Inagaki S., Kato S., J. Am. Chem. Soc., 112, 8980-8982 (1990).
44. 2 = CN) there is no significant rehybridization of the π orbital of the olefin. Rehybridization model: Inagaki S., Fukui K., Chem. Lett., 1974, 509-514; Inagaki S., Fujimoto H., Fukui K., J. Am. Chem. Soc., 98, 4054-4061 (1976); Ishida M., Beniya Y., Inagaki S., Kato S., J. Am. Chem. Soc., 112, 8980-8982 (1990).
45. 2 = CN) there is no significant rehybridization of the π orbital of the olefin. Rehybridization model: Inagaki S., Fukui K., Chem. Lett., 1974, 509-514; Inagaki S., Fujimoto H., Fukui K., J. Am. Chem. Soc., 98, 4054-4061 (1976); Ishida M., Beniya Y., Inagaki S., Kato S., J. Am. Chem. Soc., 112, 8980-8982 (1990).
46. Binkley J. S., Pople J. A., Hehre W. J., J. Am. Chem. Soc., 102, 939-947 (1980).
47. Epiotis N. D., Cherry W. R., Shaik S., Yates R L., Bernardi F., "Structural Theory of Organic Chemistry," (Topics in Current Chemistry 70), Springer-Verlag, Berlin, Heidelberg, 1977.
48. a) Fukui K., "Theory and Orientation and Stereoselection," Springer-Verlag, Berlin, Heidelberg, 1975; Fleming I., "Frontier Orbitals and Organic Chemical Reactions," John Wiley & Son, 1976;
49. a) Fukui K., "Theory and Orientation and Stereoselection," Springer-Verlag, Berlin, Heidelberg, 1975; Fleming I., "Frontier Orbitals and Organic Chemical Reactions," John Wiley & Son, 1976;
50. b) Henri-Rousseau O., Texier F., J. Chem. Educa., 55, 437-441 (1978).
51. In order to emphasize electron density distribution of the internuclear region of the less-diffused orbital state in addition to the phase relation of the interacting orbitals, we adopted the diagrams depicted in (i) and (ii). See references 19 and 20. (Matrix Presented) Unsymmetrization of π Orbital of the Olefin Arising from Antibonding Interaction
52. Fukui K., Bull. Chem. Soc., Jpn., 39, 498-507 (1966).
53. 2) fragment, although the group electronegativity is higher in the CX portion. This can be seen in the drawing.
54. C-CX Orbital of Ethane Substituted with an Electron-withdrawing Group can interact with the vacant aromatic π* orbitals (NXLUMO or LUMO) of the aromatic moiety, e.g., dihydroanthracene in the case of 3, which creates a bonding region. When the substituent is electron-withdrawing, the aromatic π* orbitals of the substituted benzene have lowered energy, and thus the π-π* interaction is activated on the side of the substituent. This can at least partially explain the observed syn-preference inherent to electron-with-drawing substituents in 3 and other systems.
55. Pfaendler H. R., Tanida H., Haselback E., Helv Chim. Acta, 57, 383-394 (1974).
56. Bader R. W., "Atoms in Molecules. A Quantum Theory," Oxford University Press, Oxford, 1990.
57. Wiberg K. B., Bader R. F. W., Lau C. D. H., J. Am. Chem. Soc., 109, 985-1001 (1987); Idem, ibid., 109, 1001-1012 (1987).
58. Wiberg K. B., Bader R. F. W., Lau C. D. H., J. Am. Chem. Soc., 109, 985-1001 (1987); Idem, ibid., 109, 1001-1012 (1987).
59. See also Inagaki S., Goto N., Yoshikawa K., J. Am. Chem. Soc., 113, 7144-7146 (1991).
60. Mulliken R. S., J. Chem. Phys., 23, 1833-1840 (1955); idem, ibid., 23, 1841-1846 (1955); idem, ibid., 23, 2338-2342 (1955); idem, ibid., 23, 2343-2346 (1955)
61. Mulliken R. S., J. Chem. Phys., 23, 1833-1840 (1955); idem, ibid., 23, 1841-1846 (1955); idem, ibid., 23, 2338-2342 (1955); idem, ibid., 23, 2343-2346 (1955)
62. Mulliken R. S., J. Chem. Phys., 23, 1833-1840 (1955); idem, ibid., 23, 1841-1846 (1955); idem, ibid., 23, 2338-2342 (1955); idem, ibid., 23, 2343-2346 (1955)
63. Mulliken R. S., J. Chem. Phys., 23, 1833-1840 (1955); idem, ibid., 23, 1841-1846 (1955); idem, ibid., 23, 2338-2342 (1955); idem, ibid., 23, 2343-2346 (1955)
64. NMR studies of norbornanes: Grutzner J. B., Jauielat M. Dence J. B., Smith R. A., Roberst J. D., J. Am. Chem. Soc., 92, 7107-7120 (1970), Bicker R., Kessler H., Zimmermann G., Chem. Ber., 111, 3200-3214 (1978); Hoffmann R. W., Kurz H., Ibid., 108, 119-127 (1975); Bicker R., Kessler H., Steigel A., Zimmermann G., ibid., 111, 3215-3221 (1978); Hoffmann R. W., Hauel N., Landmann B., ibid., 116, 389-103 (1983); Marchand A. P., "Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems," Verlag Chemie International Inc., Florida, 1982; Breitmaier E., Voelter W., "Carbon-13 NMR Spectroscopy: High-resolution Methods and Applications in Organic Chemistry and Biochemistry," 3rd ed., Weinheim, VCH, 1987.
65. NMR studies of norbornanes: Grutzner J. B., Jauielat M. Dence J. B., Smith R. A., Roberst J. D., J. Am. Chem. Soc., 92, 7107-7120 (1970), Bicker R., Kessler H., Zimmermann G., Chem. Ber., 111, 3200-3214 (1978); Hoffmann R. W., Kurz H., Ibid., 108, 119-127 (1975); Bicker R., Kessler H., Steigel A., Zimmermann G., ibid., 111, 3215-3221 (1978); Hoffmann R. W., Hauel N., Landmann B., ibid., 116, 389-103 (1983); Marchand A. P., "Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems," Verlag Chemie International Inc., Florida, 1982; Breitmaier E., Voelter W., "Carbon-13 NMR Spectroscopy: High-resolution Methods and Applications in Organic Chemistry and Biochemistry," 3rd ed., Weinheim, VCH, 1987.
66. NMR studies of norbornanes: Grutzner J. B., Jauielat M. Dence J. B., Smith R. A., Roberst J. D., J. Am. Chem. Soc., 92, 7107-7120 (1970), Bicker R., Kessler H., Zimmermann G., Chem. Ber., 111, 3200-3214 (1978); Hoffmann R. W., Kurz H., Ibid., 108, 119-127 (1975); Bicker R., Kessler H., Steigel A., Zimmermann G., ibid., 111, 3215-3221 (1978); Hoffmann R. W., Hauel N., Landmann B., ibid., 116, 389-103 (1983); Marchand A. P., "Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems," Verlag Chemie International Inc., Florida, 1982; Breitmaier E., Voelter W., "Carbon-13 NMR Spectroscopy: High-resolution Methods and Applications in Organic Chemistry and Biochemistry," 3rd ed., Weinheim, VCH, 1987.
67. NMR studies of norbornanes: Grutzner J. B., Jauielat M. Dence J. B., Smith R. A., Roberst J. D., J. Am. Chem. Soc., 92, 7107-7120 (1970), Bicker R., Kessler H., Zimmermann G., Chem. Ber., 111, 3200-3214 (1978); Hoffmann R. W., Kurz H., Ibid., 108, 119-127 (1975); Bicker R., Kessler H., Steigel A., Zimmermann G., ibid., 111, 3215-3221 (1978); Hoffmann R. W., Hauel N., Landmann B., ibid., 116, 389-103 (1983); Marchand A. P., "Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems," Verlag Chemie International Inc., Florida, 1982; Breitmaier E., Voelter W., "Carbon-13 NMR Spectroscopy: High-resolution Methods and Applications in Organic Chemistry and Biochemistry," 3rd ed., Weinheim, VCH, 1987.
68. NMR studies of norbornanes: Grutzner J. B., Jauielat M. Dence J. B., Smith R. A., Roberst J. D., J. Am. Chem. Soc., 92, 7107-7120 (1970), Bicker R., Kessler H., Zimmermann G., Chem. Ber., 111, 3200-3214 (1978); Hoffmann R. W., Kurz H., Ibid., 108, 119-127 (1975); Bicker R., Kessler H., Steigel A., Zimmermann G., ibid., 111, 3215-3221 (1978); Hoffmann R. W., Hauel N., Landmann B., ibid., 116, 389-103 (1983); Marchand A. P., "Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems," Verlag Chemie International Inc., Florida, 1982; Breitmaier E., Voelter W., "Carbon-13 NMR Spectroscopy: High-resolution Methods and Applications in Organic Chemistry and Biochemistry," 3rd ed., Weinheim, VCH, 1987.
69. NMR studies of norbornanes: Grutzner J. B., Jauielat M. Dence J. B., Smith R. A., Roberst J. D., J. Am. Chem. Soc., 92, 7107-7120 (1970), Bicker R., Kessler H., Zimmermann G., Chem. Ber., 111, 3200-3214 (1978); Hoffmann R. W., Kurz H., Ibid., 108, 119-127 (1975); Bicker R., Kessler H., Steigel A., Zimmermann G., ibid., 111, 3215-3221 (1978); Hoffmann R. W., Hauel N., Landmann B., ibid., 116, 389-103 (1983); Marchand A. P., "Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems," Verlag Chemie International Inc., Florida, 1982; Breitmaier E., Voelter W., "Carbon-13 NMR Spectroscopy: High-resolution Methods and Applications in Organic Chemistry and Biochemistry," 3rd ed., Weinheim, VCH, 1987.
70. NMR studies of norbornanes: Grutzner J. B., Jauielat M. Dence J. B., Smith R. A., Roberst J. D., J. Am. Chem. Soc., 92, 7107-7120 (1970), Bicker R., Kessler H., Zimmermann G., Chem. Ber., 111, 3200-3214 (1978); Hoffmann R. W., Kurz H., Ibid., 108, 119-127 (1975); Bicker R., Kessler H., Steigel A., Zimmermann G., ibid., 111, 3215-3221 (1978); Hoffmann R. W., Hauel N., Landmann B., ibid., 116, 389-103 (1983); Marchand A. P., "Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems," Verlag Chemie International Inc., Florida, 1982; Breitmaier E., Voelter W., "Carbon-13 NMR Spectroscopy: High-resolution Methods and Applications in Organic Chemistry and Biochemistry," 3rd ed., Weinheim, VCH, 1987.
71. Gassman P G., Talley J. J., J. Am. Chem. Soc., 102, 1214-1216 (1980).
72. Lowry T. H., Richardson K. S., "Mechanism and Theory in Organic Chemistry," 3rd ed., Harper Collins Publisher, New York, 1987, Chapter 2.
73. Cieplak A. S., Tait B. D., Johnson C. R., J. Am. Chem. Soc., 111, 8447-8462 (1989).
74. a) Chérest M., Felkin H., Prudent N., Tetrahedron Lett., 1968, 2199-2204;
75. b) Chérest M., Felkin H., ibid., 1968, 2205-2208.
76. Anh N. T., Eisenstein O., Nouv. J. Chem., 1, 61-70 (1977).
77. Grob C. A., Sawlewicz P., Helv. Chim Acta, 67, 1859-1867 (1984).
78. Tori K., Kitahonoki K., Takano Y., Tanida H., Tsuji T. Tetrahedron Lett., 1964, 559-564.
79. Gaussian 92: Frisch M. J., Trucks G. W., Head-Gordon M., Gill P. M. W., Wong M. W., Foresman J. B., Johnson B. G., Schlegel H. B., Robb M. A., Replogle E S., Gomperts R., Andres 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.
80. PSI88, version 1.0., Jorgensen W. L., Severance D. L., Department of Chemistry, Yale University, U. S. A.
81. Jorgensen W. L , Salem L , "The Organic Chemist's Book of Orbitals," Academic Press, New York, 1973.
82. We thank Professor Koop Lammerstma, Department of Chemistry, University of Alabama at Birmingham, for the program SADDLE.