A non-cope among the cope rearrangements of 1,3,4,6-tetraphenylhexa-1,5- dienes

Journal of the American Chemical Society

Volumn 122, Issue 2, 2000, Pages 193-203

  Doering, W V E ^a   Birladeanu, Ludmila ^a   Sarma, Keshab ^a   Blaschke, G ^b   Scheidemantel, Ursula ^b   Boese, R ^c   Benet Bucholz, Jordi ^c   Klarner F G ^c   Gehrke, Jan Stephan ^c   Zimny, Bernd Ulrich ^c   Sustmann, R ^c   Korth, Hans Gert ^c  

^a HARVARD UNIVERSITY   (United States)

^b UNIVERSITY OF MÜNSTER   (Germany)

^c UNIVERSITY OF DUISBURG ESSEN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; ELECTRON SPIN RESONANCE; REACTION ANALYSIS; THERMODYNAMICS;

EID: 0033978664     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993417h     Document Type: Article

References (70)

1. (a) Cope, A. C.; Hardy, E. M. J. Am. Chem. Soc. 1940, 62, 441-444.
2. (b) Cope, A. C.; Hoyle, K. E.; Heyl, D. J. Am. Chem. Soc. 1941, 63, 1843-1852.
3. (c) Cope, A. C.; Hofmann, C. M.; Hardy, E. M. J. Am. Chem. Soc. 1941, 63, 1852-1857.
4. (d) Whyte, D. E.; Cope, A. C. J. Am. Chem. Soc. 1943, 65, 1999-2004.
5. (e) Levy, H.; Cope, A. C. J. Am. Chem. Soc. 1944, 66, 1684-1688.
6. (f) Foster, E. G.; Cope, A. C.; Daniels, F. J. Am. Chem. Soc. 1947, 69, 1893-1896.
7. 3
8. Gajewski, J. J.; Benner, C. W.; Hawkins, C. M. J. Org. Chem. 1987, 52, 5198-5204.
9. (a) Koch, H. P. J. Chem. Soc. 1948, 1111-1117.
10. (b) Lutz, R. P.; Bernal, S.; Harris, R. O.; McNicholas, M. W. J. Am. Chem. Soc. 1971, 93, 3985-3990.
11. (c) Lutz, R. P.; Berg, H. A. J. J. Org. Chem. 1980, 45, 3915-3916.
12. (d) Diedrich, M. K.; Hochstrate, D.; Klärner, F.-G.; Zimny, B. Angew. Chem., Int. Ed. Engl. 1994, 33, 1079-1081.
13. (a) Dewar, M. J. S.; Ford, G. P.; McKee, M. L.; Rzepa, H. S.; Wade, L. E., Jr. J. Am. Chem. Soc. 1977, 99, 5069-5073.
14. (b) Dewar, M. J. S.; Wade, L. E., Jr. J. Am. Chem. Soc. 1977, 99, 4417-4424.
15. Doering, W. von E.; Toscano, V. G.; Beasley, G. H. Tetrahedron 1971, 27, 5299-5306.
16. Doering, W. von E.; Wang, Y.-h. J. Am. Chem. Soc. 1999, 121, 10112-10118.
17. Doering, W. von E.; Benkhoff, J.; Carleton, P. S.; Pagnotta, M. J. Am. Chem. Soc. 1997, 119, 10947-10955.
18. Doering, W. von E.; Birladeanu, L.; Sarma, K.; Teles, J. H.; Klärner, F.-G.; Gehrke, J.-S. J. Am. Chem. Soc. 1994, 116, 4289-4297.
19. 11
20. Among numerous examples, see Roth, W. R.; Gleiter, R.; Paschmann, V.; Hackler, U. E.; Fritzsche, G.; Lange, H. Eur. J. Org. Chem. 1998, 961-967.
21. Roth, W. R.; Bauer, F.; Beitat, A.; Ebbrecht, T.; Wüstefeld, M. Chem. Ber. 1991, 124, 1453-1460.
22. -1.
23. Roth, W. R.; Lennartz, H.-W.; Doering, W. v. E.; Birladeanu, L.; Guyton, C. A.; Kitagawa, T. J. Am. Chem. Soc. 1990, 112, 1722-1732.
24. Bergmann, E.; Ukai, T. Chem. Ber. 1933, 66, 54-58.
25. Vögtle, F.; Goldschmitt, E. Chem. Ber. 1976, 109, 1-40.
26. Boche, G.; Schneider, D. R. Angew. Chem., Int. Ed. Engl. 1977, 16, 869-870.
27. Brock, C. P.; Dunitz, J. D. Chem. Mater. 1994, 6, 1118-1127.
28. Structural assignments are reversed in ref 17.
29. Burkert, U.; Allinger, N. L. Computational Chemistry; American Chemical Society: Washington, DC, 1982. Cambridge Scientific Computing, Inc., Cambridge, MA 02139: Chem 3D 3.0.1.
30. Allinger, N. L.; Yuh, Y. H.; Lii, J.-H. J. Am. Chem. Soc. 1989, 111, 8551-8566.
31. Corbally, R. P.; Perkins, M. J.; Elnitski, A. P. J. Chem. Soc., Perkin Trans. 1 1979, 793-798.
32. Herberg, C.; Beckhaus, H.-D.; Körtvelyes, T.; Rüchardt, C. Chem. Ber. 1993, 123, 117-127.
33. (a) Landolt-Bernstein, New Series, Magnetic Properties of Free Radicals, Vol. II/17cb; Fischer, H., Hellwege, K. H., Eds.; Springer: Berlin, 1989; p 25 ff;
34. (b) Landolt-Bernstein, New Series, Magnetic Properties of Free Radicals, Vol. II/9b; Fischer, H., Hellwege, K. H., Eds.; Springer: Berlin, 1977; p 392.
35. An energetically implausible chain mechanism involving 1,3-diphenylallyl radical as carrier finds no support in the failure of additions of AIBN or iodine to accelerate the reaction.
36. 2", Shaker Verlag: Postfach 1290, D-52013 Aachen, Germany.
37. Klärner, F.-G. Chem. Uns. Zeit 1989, 23, 53-63. Klärner, F.-G.; Krawczyk, B.; Ruster, V.; Deiters, U. K. J. Am. Chem. Soc. 1994, 116, 7646-7657. Klärner, F.-G.; Diederich, M. K.; Wigger, A. E. Effect of Pressure on Organic Reactions. In Chemistry under Extreme or Nonclassical Conditions; van Eldik, R., Hubbard, C. D., Eds; Wiley: New York, Spektrum: Heidelberg, 1997; Chapter 3, pp 103-161.
38. Klärner, F.-G. Chem. Uns. Zeit 1989, 23, 53-63. Klärner, F.-G.; Krawczyk, B.; Ruster, V.; Deiters, U. K. J. Am. Chem. Soc. 1994, 116, 7646-7657. Klärner, F.-G.; Diederich, M. K.; Wigger, A. E. Effect of Pressure on Organic Reactions. In Chemistry under Extreme or Nonclassical Conditions; van Eldik, R., Hubbard, C. D., Eds; Wiley: New York, Spektrum: Heidelberg, 1997; Chapter 3, pp 103-161.
39. Klärner, F.-G. Chem. Uns. Zeit 1989, 23, 53-63. Klärner, F.-G.; Krawczyk, B.; Ruster, V.; Deiters, U. K. J. Am. Chem. Soc. 1994, 116, 7646-7657. Klärner, F.-G.; Diederich, M. K.; Wigger, A. E. Effect of Pressure on Organic Reactions. In Chemistry under Extreme or Nonclassical Conditions; van Eldik, R., Hubbard, C. D., Eds; Wiley: New York, Spektrum: Heidelberg, 1997; Chapter 3, pp 103-161.
40. W/V): Asano, T.; le Noble, W. J. Rev. Phys. Soc. Jpn. 1973, 43, 82-91. Yoshimura, Y.; Osugi, J.; Nakahara, M. Bull. Chem. Soc. Jpn. 1983, 56, 680-683. Yoshimura, Y.; Osugi, J.; Nakahara, M. J. Am. Chem. Soc. 1983, 105, 5414-5418.
41. W/V): Asano, T.; le Noble, W. J. Rev. Phys. Soc. Jpn. 1973, 43, 82-91. Yoshimura, Y.; Osugi, J.; Nakahara, M. Bull. Chem. Soc. Jpn. 1983, 56, 680-683. Yoshimura, Y.; Osugi, J.; Nakahara, M. J. Am. Chem. Soc. 1983, 105, 5414-5418.
42. W/V): Asano, T.; le Noble, W. J. Rev. Phys. Soc. Jpn. 1973, 43, 82-91. Yoshimura, Y.; Osugi, J.; Nakahara, M. Bull. Chem. Soc. Jpn. 1983, 56, 680-683. Yoshimura, Y.; Osugi, J.; Nakahara, M. J. Am. Chem. Soc. 1983, 105, 5414-5418.
43. Exner, O. In Organic High-Pressure Chemistry; le Noble, W. J., Ed.; Elsevier: Amsterdam, 1988; pp 19-49.
44. -1.
45. Dierkes, G.; Klärner, F.-G.; Rüchardt, C., unpublished results.
46. 4d
47. 26 based on data (their Table 9) obtained in supercritical carbon dioxide starting with (E,E)-isomers, but not the (E,Z)-isomers. Calculation of the ratios of the concentrations of meso-(E,E)-1 and rac-(E,Z)-1 from their data reveals that, for all but the first point at all temperatures, the ratios are equilibrium ratios and have no kinetic value. As a consequence, the calculated activation parameters ascribed to this rearrangement refer to the more slowly interconverting (E,E)-isomer.
48. -1, the difference in enthalpy of formation in solution at ∼250 °C (ESR) between compounds 1 and two (E,E)-1,3-diphenylallyl radicals, is too much higher than the enthalpy of activation of racemization credibly to admit the homolytic-colligative mechanism.
49. Roth, W. R.; Staemmler, V.; Neumann, M.; Schmuck, C. Liebigs Ann. 1995, 1061-1118.
50. 35
51. Doering, W. v. E.; Sarma, K. J. Am. Chem. Soc. 1992, 114, 6037-6043.
52. Hrovat, D. A.; Beno, B. R.; Lange, H.; Yoo, H.-Y.; Houk, K. N.; Borden, W. T. J. Am. Chem. Soc. 1999, 121, 10529-10537.
53. -1, respectively.
54. Professor Weston Thatcher Borden has found that two rigidly planar allyl radicals brought together in the usual chairlike conformation have a bonding distance of ∼2.6 Å, and a bonding energy the magnitude of which varies understandably with the level of theory applied in the calculation. We express our gratitude for this calculation and permission to cite.
55. Seakins, P. W.; Pilling, M. J.; Niiranen, J. T.; Gutman, D.; Krasnaperov, L. N. J. Phys. Chem. 1992, 96, 9847-9855.
56. Consider, for example, what compounds such as optically active (R,R)- or (R,S)-(E,E)-1,4-diphenyl-3,6-di-p-tolylhexa-1,5-diene have to offer!
57. Meerwein, H.; Schmidt, R. Liebigs Ann. 1928, 444, 221-238.
58. Truett, W. L.; Moulton, W. N. J. Am. Chem. Soc. 1951, 73, 5913-5915.
59. Raunio, E. K.; Bonner, W. A. J. Org. Chem. 1966, 31, 396-399.
60. Marquardt, D. W. J. Soc. Ind. Appl. Math. 1963, 11, 431-441. We thank Dr. R. Fink for a copy of the program KINETIK, which permits optimization by the Marquardt procedure of kinetic schemes with up to seven components.
61. Stenhouse, J. Proc. R. Soc. London 1869, 17, 63. Yiannios, C. N.; Karabinos, J. V. J. Org. Chem. 1963, 28, 3246-3248.
62. Stenhouse, J. Proc. R. Soc. London 1869, 17, 63. Yiannios, C. N.; Karabinos, J. V. J. Org. Chem. 1963, 28, 3246-3248.
63. Aldrich Library of FT IR Spectra, 1st ed.; Aldrich Chemical Company; vol. 1, p 1183c. Aldrich Library of NMR Spectra, 2nd ed.; Aldrich Chemical Company, 1983; vol. 1, p 973D.
64. Aldrich Library of FT IR Spectra, 1st ed.; Aldrich Chemical Company; vol. 1, p 1183c. Aldrich Library of NMR Spectra, 2nd ed.; Aldrich Chemical Company, 1983; vol. 1, p 973D.
65. 2-carbon atom left free. Further restrictions included only those structures with an R value of < 10% and C-C esd values of <0.01 Å. The search was performed with the 3D Search and Research Using the Cambridge Structural Database: Allen, F. H.; Kennard, O. Chemical Design Automation News 1993, 8, 1831-1837.
66. Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100. Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989. Becke, A. D. J. Chem. Phys. 1993, 98, 1372, 5648-5652. Stephens, P. J.; Devlin, F. J.; Chabalowsky, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
67. Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100. Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989. Becke, A. D. J. Chem. Phys. 1993, 98, 1372, 5648-5652. Stephens, P. J.; Devlin, F. J.; Chabalowsky, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
68. Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100. Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989. Becke, A. D. J. Chem. Phys. 1993, 98, 1372, 5648-5652. Stephens, P. J.; Devlin, F. J.; Chabalowsky, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
69. Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100. Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989. Becke, A. D. J. Chem. Phys. 1993, 98, 1372, 5648-5652. Stephens, P. J.; Devlin, F. J.; Chabalowsky, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
70. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision B.2: Gaussian, Inc.; Pittsburgh, PA, 1995.