Bulletin of the Korean Chemical Society

  • 제23권6호
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  • Pages.829-837
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  • 2002
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Elucidation of Selectivity Difference in the Diels-Alder Reactions of 6,6-Disubstituted Cyclohexa-2,4-dienone

  • 발행 : 2002.06.20
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초록

Recently it was reported that cycloaddition of 6,6-disubstituted cyclohexa-2,4-dienone, 1 with cyclopentadiene gave solely the adduct of type 1.while its reaction with 1,3-cyclohexadiene gave both Ⅱ and Ⅲ. Semiempirical MO calculations were done to elucidate the origin of the selectivity difference between the two dienes. Cycloaddition of 1 with cyclopentadiene is controlled thermodynamically to give only 1-diene adduct by ΔGvalues of 10.6-20.3 kcal/mol, while its reaction with 1,3-cyclohexadiene does not show 1-diene/1-dienophile selectivity due to similar stabilities of the two adducts. Thermodynamic parameters also show that 두애 adducts are more fabourably fromed in the cycloadditions of 1 with both cyclopentadiene and 1,3-cyclohexadiene, which coincides with experimental observations. Cope rearrangements of endo adducts are another avenue to convert between 1-diene and 1-dienophile.

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참고문헌

  1. Rigby, J. H. Comprehensive Organic Synthesis; Trost, B. M, Flemming, I., Paquette, L. A., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, pp 617-643.
  2. Liu, C. Y; Ding, S. T. J. Org. Chem. 1992, 57, 4539. https://doi.org/10.1021/jo00042a039
  3. Rigby, J. H.; Ateeg, H. S. J. Am. Chem. Soc. 1990,112, 6442. https://doi.org/10.1021/ja00173a067
  4. Wender, P. A.; Correia, C. R. D. J. Am. Chem. Soc. 1987, 109, 2523. https://doi.org/10.1021/ja00242a053
  5. Garst, M. E.; Roberts, V A.; Prussin, C. J. Org. Chem. 1982, 47, 3969. https://doi.org/10.1021/jo00141a032
  6. Haseltine, J. N.; Cabel, M. P.; Mantlo, N. B.; Iwasawa, N.; Yamasita, D. S.; Coleman, R. S.; Danishefsky, S.; Schulte, G. K. J. Am. Chem. Soc. 1991,113, 3850. https://doi.org/10.1021/ja00010a030
  7. Corey, E. J.; Dittami, J. P. J. Am.Chem.Soc. 1985,107, 256. https://doi.org/10.1021/ja00287a049
  8. Singh, V. K.; Thomas, B. J. Chem. Soc, Chem. Commun. 1992, 1211.
  9. Singh, V. K.; Porinchu, M. J. Chem. Soc, Chem. Commun. 1993, 134.
  10. Sing, V.; Porinchu, M. Tetrahedron 1996, 52, 7087. https://doi.org/10.1016/0040-4020(96)00329-8
  11. Singh, V.; Thomas, B. J. Org. Chem. 1997, 62, 5310. https://doi.org/10.1021/jo9702296
  12. Singh, V.; Thomas, B. J. Indian Chem. Soc. 1998, 75, 640.
  13. Bratby, D. M; Fray, G. I. J. Chem. Soc. (C) 1971, 970.
  14. Bratby, D. M; Chadwick, J. C; Fray, G. I.; Saxton, R. G. Tetrahedron 1977, 33,1521. https://doi.org/10.1016/0040-4020(77)88017-4
  15. Gesson, J. P.; Hervaud, L.; Mondon, M. Tetrahedron Lett. 1993, 34, 2941. https://doi.org/10.1016/S0040-4039(00)60487-2
  16. Bonnarme, V.; Bachmann, C; Cousson, A.; Mondon, M; Gesson, J. P. Tetrahedron 1999, 55, 433. https://doi.org/10.1016/S0040-4020(98)01041-2
  17. Woodward, R. B.; Hoffman, R. Conservation of Orbital Symmetry; Academic Press: New York, 1972; pp 65-113.
  18. Fleming, I. Frontier Orbitals and Organic Chemical Reactions; John Wiely and Sons: Chichester, 1978; Chapter 4, pp 86-181.
  19. Carruthers, W. Some Modern Methods of Organic Synthesis; Cambridge University Press: Cambridge, 1985; Chapter 3, pp 184-262.
  20. Singh, V. K.; Deota, P. T; Bedekar, A. V. J. Chem. Soc. Perkin Trans. I 1992, 903.
  21. Singh, V.; Sharma, U.; Prasanna, V.; Porinchu, M. Tetrahedron 1995, 51, 6015. https://doi.org/10.1016/0040-4020(95)00261-6
  22. March, J. Advanced Organic Chemistry, 3rd ed.; John Wiley and Sons: New York, 1985; pp 745-758.
  23. Stewart, J. J. P. J. Comput. Chem. 1989,10, 209, 221. https://doi.org/10.1002/jcc.540100209
  24. Stewart, J. J. P.MOPAC93; Fujitsu Limited: Tokyo, 1993.
  25. Cerjan, C. J.; Miller, W H. J. Chem. Phys. 1981, 75, 2800. https://doi.org/10.1063/1.442352
  26. Banerjee, A.; Adams, A.; Simons, J.; Shepard, R. J. Phys. Chem. 1985, 89, 52. https://doi.org/10.1021/j100247a015
  27. Gonzalez, C; Schlegel, H. B. J. Phys. Chem. 1989, 93, 2154.
  28. Gonzalez, C; Schlegel, H. B. J. Phys. Chem. 1990, 94, 5523. https://doi.org/10.1021/j100377a021
  29. Mok, K. L.; Nye, M. J. J. Chem. Soc, Perkin I 1975, 1810.

피인용 문헌

  1. ChemInform Abstract: Elucidation of Selectivity Difference in the Diels-Alder Reactions of 6,6-Disubstituted Cyclohexa-2,4-dienone vol.33, pp.43, 2010, https://doi.org/10.1002/chin.200243026
  2. -Quinol Dimers vol.76, pp.21, 2011, https://doi.org/10.1021/jo201658y
  3. Epoxidation of the products of codimerization of cyclopentadiene and cyclohexadiene hydrocarbons catalyzed by lanthanide-molybdenum polyoxometalates vol.85, pp.5, 2015, https://doi.org/10.1134/S1070363215050035
  4. Epoxidation and oxidative dihydroxylation of C10–C13 unsaturated bridged hydrocarbons involving hydrogen peroxide and modified forms of heteromolybdic compounds vol.57, pp.5, 2017, https://doi.org/10.1134/S0965544117050024
  5. Regioselective Multicomponent Synthesis of 2,4,6‐Trisubstituted Phenols from Fischer Alkynyl Carbene Complexes vol.2016, pp.7, 2002, https://doi.org/10.1002/ejoc.201501211