Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.$2^{2,5}$ ]dodeca-1,5-diene
Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.$2^{2,5}$ ]dodeca-1,5-diene
Potential energy surface (PES) of the tricyclo[4.2.2.$2^{2,5}$ ]dodeca-1,5-diene (TCDD)-$CI_2$ system was studied by B3LYP/6-311+G(d,p) method and the configurations [reactants, molecular charge-transfer (CT) complex, transition states (TS1 and TS2), intermediate (INT), and product (P)] corresponding to the stationary points (minima or saddle points) were determined. Initially, a molecular CT-complex forms between $CI_2$ and TCDD. With a barrier of 22.362 kcal ${mol^-1}$ the CT-complex can be activated to an intermediate (INT) with energy 14.682 kcal ${mol^-1}$ higher than that of the CT-complex. The intermediate (INT) then transforms easily (barrier 5.102 kcal ${mol^-1}$) into the final, N-type product. Accompanying the breaking of the Cl-Cl bond, C1-Cl, C5-Cl and C2-C6 bonds are formed, and C1=C2 and C5=C6 double bonds transform into single bonds. The direction of the reaction is determined by the direction of the intramolecular skeletal rearrangement that is realized by the formation of the C2-C6 bond.
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- 1. Osawa, E.; Aigami, K.; Inamoto, Y. Tetrahedron 1978, 34, 509-515.
- 2. Lin, C. T.; Wang, N. J.; Yeh, Y. L.; Chou, T. C. Tetrahedron 1995, 51, 2907-2928.
- 3. Lin, C. T.; Wang, N. J.; Tseng, H. Z.; Chou, T. C. J. Org. Chem. 1997, 62, 4857-4861.
- 4. Lin, C.T.; Hsu H. C.; Chou, T. C. J. Org. Chem. 1999, 64, 7260-7264.
- 5. Soloway, S. B.; Damiana, A. M.; Sim, J. W.; Bluestone, H.; Lidov, R. E. J. Am. Chem. Soc. 1960, 82, 5377-5385.
- 6. Franz, H. J.; Hobold, W.; Hohn, R.; Muller-Hagen, G.; Muller, R.; Pritzkow, R.; Schmidt H. J. Prakt. Chem. 1970, 320, 622-634.
- 7. Sasaki, T.; Kanematsu, K.; Kondo, A. J. Org. Chem. 1974, 39, 2247-2251.
- 8. Haufe, G.; Kleinpeter, E.; Muhlstadt, M.; Graefe, J. Monatsh. Chem. 1978, 109, 575-585.
- 9. Matturro, M. G.; Adams, R. D.; Wiberg, K. B. Chem. Commun. 1981, 17, 878-879.
- 10. Uemura, S.; Fukuzawa, S.; Toshimitsu, A.; Masaya, O. J. Org. Chem. 1983, 48, 270- 273.
- 11. Wiberg, K. B.; Matturro, M. G.; Okarma, P. J.; Jason, M. E. J. Am. Chem. Soc. 1984, 106, 2194-2200.
- 12. Wiberg, K. B.; Adams, R. D.; Okarma, P. J.; Matturro, M. G.; Segmiller, B. J. Am. Chem. Soc. 1984, 106, 2200-2206.
- 13. Kimura, M.; Morossawa, S. J. Org. Chem. 1985, 50, 1532-1534.
- 14. Shea, K. J.; Greeley, A. C.; Nguyen, S.; Beauchamp, P. D.; Aue, D. H.; Witzeman, J. S. J. Am. Chem. Soc. 1986, 108, 5901-5908.
- 15. Haufe, G.; Alvernhe, G.; Laurent, A. Tetrahedron Lett. 1986, 27, 4449-4452.
- 16. Murty, B.A.R.C.; Pinkos, R.; Spurr, P. R.; Fessner, W. D.; Lutz, G.; Fritz, H.; Hunkler, D.; Prinzbach, H. Chem. Ber. 1992, 125, 1719-1739.
- 17. Pinkos, R.; Melder, J. P; Weber, K.; Hunkler, D.; Prinzbach, H. J. Am. Chem. Soc. 1993, 115, 7173-7191.
- 18. Herges, R.; Neumann, H. Liebigs Ann. 1995, 1283-1289.
- 19. Robinson, R. E.; Myers, D. Y. Tetrahedron Lett. 1999, 40, 1099-1100.
- 20. G¨unbas, D. D.; Algı, F.; H¨okelek, T.; Watson, W. H.; Balcı M. Tetrahedron 2005, 61, 11177-11183.
- 21. Belluci, G.; Chiappe, C.; Bianchini, R. ; Lenoir, D.; Herges, R. J. J. Am. Chem. Soc. 1995, 117, 12001-12002.
- 22. Herges, R. Angew Chem. Int. Edit. Engl. 1995, 34, 51-53.
- 23. Ruiz, E.; Dennis, R.; Salahub, R.; Vela, A. J. Phys. Chem. 1996, 100,12265-12276.
- 24. Brown, R. S.; Acc. Chem. Res. 1997, 30, 131-137.
- 25. Bianchini, R.; Chiappe, C.; Lenoir, D.; Lemmen, P.; Herges, R.; Grunenberg, J. Angeew Chem. Int. Edit. Eng. 1997, 36, 1284-1287.
- 26. Smith, W. B. J. Org. Chem. 1998, 63, 2661-2664.
- 27. Bianchini, R.; Chiappe, C.; Moro, L. G.; Lenoir, D.; Lemmen, P.; Goldberg, N. Chem. Eur. J. 1999, 5, 1570-1580.
- 28. Chiappe, C.; Rubertis, A.; Lemmen, P.; Lenoir, D. J. Org. Chem. 2000, 65, 1273-1279.
- 29. Chiappe, C.; Rubertis, A. D.; Detert, H.; Lenoir, D.; Wannere, C.; Schleyer, P. R. Chem. Eur. J. 2002, 8, 967-978.
- 30. Rathere, R.; Lindeman, S. V.; Zhu, C. J.; Mori, T.; Schleyer, P. R.; Kochi, J. K. J. Org. Chem. 2002, 67, 5106-5116.
- 31. Lenoi, D.; Chiapp, C. Chem. Eur. J. 2003, 9, 1037-1044.
- 32. Chiappe, C.; Detert, H.; Lenoir, D.; Pomelli, C. S.; Ruasse, M. F. J. Am. Chem. Soc. 2003, 125, 2864-2865.
- 33. Herges, R.; Papafflippopoulos, A.; Hess, K.; Chiappe, C.; Lenoir, D.; Detert, H. Angew Chem. Int. Ed. 2005, 44, 1412-1416.
- 34. Chiappe, C.; Pomelli, C. S.; Lenoir, D.; Wattenbach, C. J. Mol. Model. 2006, 12, 631- 639.
- 35. Wang, S. C.; Tantillo, D. Eur. J. Org. Chem. 2006, 3, 738-745.
- 36. Balcı, M.; G¨uney, M.; Da¸stan, A.; Azizoglu, A. J. Org. Chem. 2007, 72, 4756-4762.
- 37. Abbasoglu, R. J. Mol. Struct. (Theochem) 2004, 686, 1-5 and references therein.
- 38. Abbasoglu, R.; Yilmaz, S.; G¨ok, Y. Indian J. Chem. 2005, 44A, 221-226.
- 39. Abbasoglu, R.; Yilmaz, S. J. Mol. Model. 2006, 12, 290-296.
- 40. Abbasoglu, R. J. Mol. Model. 2006, 12, 991-995.
- 41. Abbasoglu, R. J. Mol. Model. 2007, 13, 425-430.
- 42. Abbasoglu, R. J. Mol. Model. 2007, 13, 1215-1220.
- 43. Abbasoglu, R.; Uygur, Y. Indian J. Chem. 2007, 46A, 396-400.
- 44. Abbasoglu, R.; Magerramov, A. Acta Chim. Slov. 2007, 54, 882-887.
- 45. Abbasoglu, R.; Maggeramov, A. Acta Chim. Slov. 2009, 56, 237-245.
- 46. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. 1988, B 37, 785-789.
- 47. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
- 48. McLean, A. D.; Chandler, G. S. J. Chem. Phys. 1980, 72, 5639-5648.
- 49. Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J.A. J. Chem. Phys. 1980, 72,650-654.
- 50. Page, M.; Mclver, Jr. J. W. J. Chem. Phys. 1988, 88, 922-935.
- 51. Gonzalez, C.; Schlegel H. B. J. Phys. Chem. 1989, 90, 2154-2161.
- 52. Gonzalez, C.; Schlegel H. B. J. Phys. Chem. 1990, 94, 5523-5527.