Abstract
Possible paths of halogen atom migration in 5-halogeno-1,2,3,4,5-pentamethoxycarbonylcyclopentadienes were studied using the density functional theory. The calculations revealed preferential 1,5(in comparison with 1,3-) sigmatropic shifts of halogen atoms along the perimeter of the five-membered ring with the energy barriers ΔE ZPE ≠ = 42.9, 26.9, 19.8, and 15.4 kcal mol–1 for the fluoro-, chloro-, bromo-, and iodosubstituted derivatives, respectively. The calculated charges of halogen atoms in the structures of transition states for 1,5-shifts change from negative for the fluorine atom to positive for the iodine atom (–0.356 (F), 0.019 (Cl), 0.052 (Br), 0.184 e (I)). The migration capacity increases in the order F < Cl < Br < I with an increase in the atomic radius of halogen.
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References
M. I. Bruce, Australian J. Chem., 1990, 43, 949.
L. D. Field, C. M. Lindall, A. F. Masters, G. K. B. Clentsmith, Coord. Chem. Rev., 2011, 255, 1733.
J.-Y. Thepot, C. Lapinte, J. Organomet. Chem., 2001, 627, 179.
G. Vives, G. Rapenne, Tetrahedron, 2008, 64, 11462.
R. Breslow, J. M. Hoffman, C. Perchonock, Tetrahedron Lett., 1973, 38, 3723.
A. S. Kelch, P. G. Jones, I. Dix, H. Hopf, Beilstein J. Org. Chem., 2013, 9, 1705.
S. Magen, J. Oren, B. Fuchs, Tetrahedron Lett., 1984, 25, 3369.
R. C. Cookson, J. B. Henstock, J. Hudec, B. R. D. Whitear, J. Chem. Soc., Sect. C, 1967, 20, 1986.
I. E. Mikhailov, G. A. Dushenko, A. V. Kisin, C. Mugge, A. Zschunke, V. I. Minkin, Mendeleev Commun., 1994, 4, 85.
V. I. Minkin, I. E. Mikhailov, G. A. Dushenko, I. A. Yudilevich, A. Zschunke, K. Mugge, J. Phys. Org. Chem., 1991, 4, 31.
I. E. Mikhailov, V. I. Minkin, G. A. Dushenko, A. A. Klenkin, L. P. Olekhnovich, Zh. Org. Khim., 1988, 24, 1179 [Russ. J. Org. Chem. (Engl. Transl.), 1988, 24].
I. E. Mikhailov, G. A. Dushenko, V. I. Minkin, Vestn. Yuzh. Nauch. Tsentra [Bulletin of Southern Scientific Center], 2006, 2, 19 (in Russian).
V. I. Minkin, I. E. Mikhailov, G. A. Dushenko, A. Zschunke, Russ. Chem. Rev., 2003, 72, 867.
I. E. Mikhailov, G. A. Dushenko, V. I. Minkin, Molekulyarnye peregruppirovki tsiklopolienov [Molecular Rearrangements of Cyclopolyenes], Nauka, Moscow, 2008, 229 pp. (in Russian).
R. Breslow, J. W. Canary, J. Am. Chem. Soc., 1991, 113, 3950.
G. A. Dushenko, I. E. Mikhailov, O. I. Mikhailova, R. M. Minyaev, V. I. Minkin, Mendeleev Commun., 2015, 25, 21.
V. I. Minkin, I. E. Mikhailov, G. A. Dushenko, O. E. Kompan, A. Zschunke, Russ. Chem. Bull. (Engl. Transl.), 1998, 47, 884 [Izv. Akad. Nauk, Ser. Khim., 1998, 47, 913].
I. E. Mikhailov, O. E. Kompan, G. A. Dushenko, V. I. Minkin, Mendeleev Commun., 1991, 1, 121.
V. I. Minkin, I. E. Mikhailov, G. A. Dushenko, I. D. Sadekov, A. A. Maksimenko, Yu. E. Chernysh, Dokl. Akad. Nauk, 1992, 322, 706 [Dokl. Phys. Chem. (Engl. Transl.), 1992, 322].
I. E. Mikhailov, G. A. Dushenko, I. V. Dorogan, R. M. Minyaev, V. V. Negrebetskii, A. Zschunke, V. I. Minkin, Mendeleev Commun., 1994, 4, 9.
G. A. Dushenko, I. E. Mikhailov, A. Zschunke, N. Hakam, C. Mugge, V. I. Minkin, Mendeleev Commun., 1995, 5, 133.
G. A. Dushenko, I. E. Mikhailov, A. Zschunke, G. Reck, B. Schulz, V. I. Minkin, Mendeleev Commun., 1999, 9, 222.
S. Jayanty, D. B. K. Kumar, T.P. Radhakrishnan, Synth. Met., 2000, 114, 37.
G. Maas, H. M. Weber, R. Exner, J. Salbeck, J. Phys. Org. Chem., 1990, 3, 459.
E. Aqad, P. Leriche, G. Mabon, A. Gorgues, V. Khodorkovsky, Org. Lett., 2001, 3, 2329.
J. B. Foresman, E. Frisch, Exploring Chemistry with Electronic Structure Methods, Gaussian Inc., Pittsburg, 1996, 302 pp.
R. W. Hoffmann, J. Backes, Chem. Ber., 1976, 109, 1928.
R. Breslow, G. Ryan, J. T. Groves, J. Am. Chem. Soc., 1970, 92, 988.
Ch. W. Spangler, Chem. Rev., 1976, 76, 187.
H. Kessler, M. Feigel, Acc. Chem. Res., 1982, 15, 2.
T. Okajima, K. Imafuku, J. Org. Chem., 2002, 67, 625.
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Dedicated to Academician of the Russian Academy of Sciences N. S. Zefirov on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2043—2049, September, 2015.
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Dushenko, G.A., Mikhailov, I.E., Mikhailova, O.I. et al. Mechanisms of circumambulatory rearrangements of 5-halogeno-1,2,3,4,5-pentamethoxycarbonylcyclopentadienes. Russ Chem Bull 64, 2043–2049 (2015). https://doi.org/10.1007/s11172-015-1115-z
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DOI: https://doi.org/10.1007/s11172-015-1115-z