Stereoelectronic effect in reactions of phosphoester bond rupture

  • A. A. Voityuk
Physical Chemistry


The potential surface profile of the interaction of the anion (CH3O)2PO2 with the nucleophile CH3O in the gas phase and in aqueous solution has been calculated by the AMl method. The energy of the transition state of the reaction in the gas phase is very much dependent on the position of the equatorial methoxy group; the change in the activation barrier amounts to 6 kcal/mole. The stereoelectronic effect is due to electrostatic interaction of the dipole moment of the equatorial substituent with the charge of the attacking or leaving group. An accounting for solvation gives a considerable decrease in the stereoelectronic effect.


Aqueous Solution Transition State Dipole Moment Electrostatic Interaction Methoxy 
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Literature cited

  1. 1.
    H. Dugas and C. Penney, Bioorganic Chemistry: A Chemical Approach to Enzyme Action, Springer-Verlag, New York (1981).Google Scholar
  2. 2.
    D. G. Gorenstein, Chem. Rev.,87, 1047 (1987).Google Scholar
  3. 3.
    D. G. Gorenstein, B. A. Luxon, and J. B. Findley, J. Am. Chem. Soc.,101, 5869 (1979).Google Scholar
  4. 4.
    M. J. S. Dewar, E. Zoebisch, E. Healy, and J. J. P. Stewart, J. Am. Chem. Soc.,101, 5869 (1979).Google Scholar
  5. 5.
    M. J. S. Dewar and C. Jie, J. Mol. Struct. (Theochem),187, 1 (1989).Google Scholar
  6. 6.
    J. Baker, J. Comput. Chem.,7, 385 (1986).Google Scholar
  7. 7.
    K. Ya. Burshtein, Zh. Strukt. Khim.,28, No. 2, 3 (1987).Google Scholar
  8. 8.
    A. A. Voityuk and A. A. Bliznyuk, Izv. Akad. Nauk SSSR, Ser. Khim., No. 8, 1785 (1989).Google Scholar

Copyright information

© Plenum Publishing Corporation 1991

Authors and Affiliations

  • A. A. Voityuk
    • 1
  1. 1.Novosibirsk Institute of Bioorganic ChemistrySiberian Branch of the Academy of Sciences of the USSRUSSR

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