Abstract
On the basis of the concept of polarity (“philicity”) of free radicals as proposed by the authors, within the framework of methods of qualitative surfaces of potential energy (linear combinations of configurations of fragments) and stabilization energy, an effective model has been developed for the regioselectivity and reactivity of radicals in processes of addition. A critical examination is made of certain key aspects of the change in regiochemistry and reactivity with changes in the electronic structure of the free radical and substrate. The dominant trends in regioselectivity and reactivity in processes of free-radical addition to olefins are controlled by electronic effects and can be predicted by analyzing interactions of diabatic potential energy surfaces or orbital interactions for a system consisting of a free radical and an unsaturated substrate.
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J. M. Tedder and J. C. Walton, “The kinetics and orientation of free-radical addition to olefins,” Acc. Chem. Res., 9, No. 5, 183–191 (1976).
J. M. Tedder and J. G. Walton, “Directive effects in gas-phase radical addition reactions,” Adv. Phys. Org. Chem., 16, 51–86 (1978).
J. M. Tedder and J. C. Walton, “The importance of polarity and steric effects in determining the rate and orientation of free radical additions to olefins,” Tetrahedron, 36, No. 6, 701–707 (1980).
J. M. Tedder, “Which factors determine the reactivity and regioselectivity of free radical substitution and addition reactions,” Angew. Chem. Int. Ed., 21, No. 6, 401–410 (1982).
B. Giese, “Formation of CC bonds by addition of free radicals to alkenes,” Angew. Chem. Int. Ed., 22, No. 10, 753–764 (1983).
M. V. Bazilevskii, Molecular Orbital Method and Reactivity of Organic Molecules [in Russian], Khimiya, Moscow (1969).
M. V. Bazilevskii (Basilevsky), “Transition state stabilization energy as a measure of chemical reactivity,” Adv. Chem. Phys., 33, 345–398 (1975).
N. D. Epiotis, Theory of Organic Reactions, Springer, Berlin (1978).
I. Fleming, “Frontier orbitals and organic chemical reactions,” Wiley-Interscience, New York (1978).
J. M. Tedder and J. C. Walton, “Kinetics and mechanism of the addition of fluorine-containing radicals to olefins,” ACS Symposia, No. 66, 107–127 (1978).
M. V. Zhuravlev, V. P. Sass, and S. V. Sokolov, “Reactions of fluorine-containing alkyl radicals in solution. 4. Application of correlation analysis to addition reactions,” Zh. Org. Khim., 22, No. 1, 59–63 (1986).
S. V. Volovik, G. G. Dyadyusha, and V. I. Staninets, “Concept of polarity of free radicals in reactions of addition to olefins,” Teor. Éksp. Khim., 22, No. 5, 562–571 (1986).
K. Fukui and H. Fujimoto, “An MO-theoretical interpretation of the nature of chemical reactions. The governing principles,” Bull. Chem. Soc. Jpn., 42, No. 12, 3399–3409 (1969).
S. Nagase, K. Takatsuka, and T. Fueno, “LMO studies of chemical reactions. Deformation, rearrangement, and spin polarization of bond involved in radical reactions,” J. Am. Chem. Soc., 98, No. 13, 3838–3844 (1976).
M. J. S. Dewar, The Molecular Orbital Theory of Organic Chemistry, McGraw-Hill, New York (1969).
K. Fukui, Theory of Orientation and Stereoselection, Springer, Berlin (1975).
R. G. Parr and W. Yang, “Density functional approach to the frontier-electron theory of chemical reactivity,” J. Am. Chem. Soc., 106, No. 14, 4049–4050 (1984).
A. Pross, “The reactivity-selectivity principle and its mechanistic applications,” Adv. Phys. Org. Chem., 14, 69–132 (1977).
G. S. Hammond, “A correlation of reaction rates,” J. Am. Chem. Soc., 77, No. 2, 334–338 (1955).
K. N. Houk, J. Sims, R. E. Duke, et al., “Frontier molecular orbitals of 1,3 dipoles and dipolarophiles,” J. Am. Chem. Soc., 95, No. 22, 7287–7301 (1973).
K. N. Houk, “Applications of frontier molecular orbital theory to pericyclic reactions,” in: Pericyclic Reactions, A. P. Marchand and R. E. Lehr (eds.), Academic Press, New York (1977), Vol. 2, pp. 181–271.
K. N. Houk, “Theoretical and experimental insights into cycloaddition reactions,” Top. Curr. Chem., 79, 1–40 (1979).
H. G. Viehe, Z. Janousek, R. Merenyi, and L. Stella, “The captodative effect,” Acc. Chem. Res., 18, No. 5, 148–154 (1985).
M. N. Paddon-Row, N. G. Rondan, K. N. Houk, and K. D. Jordan, “Geometries of the radical anions of ethylene, fluoroethylene, 1,1-difluoroethylene, and tetrafluorethylene,” J. Am. Chem. Soc., 104, No. 4, 1143–1145 (1982).
K. N. Houk, “Molecular distortions and organic reactivity: Additions, cycloadditions, and free radical reactions,” in: Frontiers of Free Radical Chemistry, W. Pryor (ed.), Academic Press, New York (1980), pp. 43–71.
S. V. Volovik, G. G. Dyadyusha, and V. I. Staninets, “Polarity of radicals and orbital control of regioselectivity and reactivity in homolytic addition,” Dokl. Akad. Nauk Ukr. SSR, Ser. B, No. 4, 44–49 (1983).
S. V. Volovik, G. G. Dyadyusha, and V. I. Staninets, “Theoretical model of regioselectivity of reactions of free-radical addition,” Dokl. Akad. Nauk Ukr. SSR, Ser. B, No. 5, 46–60 (1982).
V. Bonacic-Koutecky, J. Koutecky, and L. Salem, “A theory of free radical reactions,” J. Am. Chem. Soc., 99, No. 3 842–850 (1977).
J. M. Poblet, E. Canadell, and T. Sordo, “Concerning the orientation in free radical addition to olefins,” Can. J. Chem., 61, No. 9, 2068–2069 (1983).
F. Delbecq, D. Ilavsky, N. T. Ahn, and J. M. Lefour, “Theoretical study of regioselectivity in radical additions to substituted alkenes. 1. Hydrogen addition to ethylene, vinylamine, and vinylborane,” J. Am. Chem. Soc., 107, No. 6, 1623–1631 (1985).
R. Ponec, J. Malek, W. Kuhnel, and E. Gey, “Directive effects and selectivity in radical addition reactions: A theoretical study,” J. Mol. Struct., Theochem, 110, 293–302 (1984).
E. Canadell, O. Eisenstein, G. Ohanessian, J. M. Poblet, “Theoretical analysis of radical additional reactions: On the anomalous behavior of CH3 toward fluoro-substituted olefins,” J. Phys. Chem., 89, No. 22, 4856–4861 (1985).
J. Bastide and O. Henri-Rosseau, “Cycloadditions and cyclizations involving triple bond,” in: The Chemistry of the Carbon-Carbon Triple Bond, S. Patai (ed.), Wiley-Interscience, New York (1978), Part I, pp. 447–522.
S. V. Volovik, G. G. Dyadyusha, and V. I. Stainets, “Polarity, regioselectivity, and reactivity of free radicals in reactions of addition to olefins,” Zh. Org. Khim., 22, No. 7, 1359–1374 (1986).
N. D. Epiotis, W. Cherry, S. Shaik, et al., “Structural theory of organic chemistry,” Top. Curr. Chem., 70, 1–250 (1977).
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 2, pp. 135–148, March–April, 1987.
The authors are grateful to M. V. Bazilevskii for his constructive discussion of the results obtained in this work.
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Volovik, S.V., Dyadyusha, G.G. & Staninets, V.I. Delocalization model of regioselectivity and reactivity of free radicals in reactions of addition to olefins. Theor Exp Chem 23, 128–140 (1987). https://doi.org/10.1007/BF00534572
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DOI: https://doi.org/10.1007/BF00534572