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Conformation effects in reduction of methyl-substituted cyclopentanones with 2-propanol in presence of RhCl(PPh3)3 or RuCl2(PPh3)3

Conclusions

  1. 1.

    The insertion into cycloheptanone of a methyl in either the 3 or 4 position, and also of two methyls in the 3 and 6 positions, does not affect the rate of hydrogen transfer from 2-propanol to the cycloheptanones in the presence of the triphenylphosphine complexes of Rh and Ru.

  2. 2.

    The presence of geminal dimethyl groupings in the 3 and 6 positions lowers the reduction rate of the cycloheptanones, which is explained by a shielding of the carbonyl by the axial methyls.

  3. 3.

    Conformational analysis revealed that in principle the cycloheptanone homologs differ from the homologs with smaller rings: transition of the axial substituent to the equatorial can occur without the complete inversion of the seven-membered ring. Both stereoisomers of 3, 6-dimethylcycloheptanone can exist in the equatorial form. This is in good agreement with the experimental data on the reduction rates.

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Literature cited

  1. 1.

    V. Z. Sharf, L. Kh. Freidlin, and V. N. Krutii, Izv. Akad. Nauk SSSR, Ser. Khim., 2264 (1973).

  2. 2.

    L. Kh. Freidlin, V. Z. Sharf, V. N. Krutii, and I. S. Shekoyan, Izv. Akad. Nauk SSSR, Ser. Khim., 1330 (1974).

  3. 3.

    J. A. Osborn, F. H. Jardine, J. E. Young, and G. Wilkinson, J. Chem. Soc., A, 1711 (1966).

  4. 4.

    T. A. Stephenson and G. Wilkinson, J. Inorg. Nucl. Chem.,A28, 945 (1966).

  5. 5.

    A. L. Liberman and T. V. Vasina, Dokl. Akad. Nauk SSSR,198, 1344 (1971).

  6. 6.

    A. L. Liberman and T. V. Vasina, Zh. Organ. Khim.,3, 690 (1967).

  7. 7.

    D. B. Furman, S. A. Chelmakova, T. V. Vasina, and A. L. Liberman, Izv. Akad. Nauk SSSR, Ser. Khim., 2124 (1974).

  8. 8.

    Y. Sasson, J. Blum, and E. Dunkelblum, Tetrahedron Lett., 3199 (1973).

  9. 9.

    V. Z. Sharf, L. Kh. Freidlin, V. N. Krutii, and T. V. Lysyak, Izv. Akad. Nauk SSSR, Ser. Khim., 2195 (1975).

  10. 10.

    N. L. Allinger, J. Am. Chem. Soc.,81, 5727 (1959).

  11. 11.

    A. L. Liberman and T. V. Vasina, Izv. Akad. Nauk SSSR, Ser. Khim., 854 (1975).

  12. 12.

    J. B. Hendrickson, J. Am. Chem. Soc.,83, 4537 (1961).

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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1111–1115, May, 1975.

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Krutii, V.N., Chelmakova, S.A., Gurovets, A.S. et al. Conformation effects in reduction of methyl-substituted cyclopentanones with 2-propanol in presence of RhCl(PPh3)3 or RuCl2(PPh3)3 . Russ Chem Bull 24, 1019–1022 (1975). https://doi.org/10.1007/BF00922956

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Keywords

  • Reduction Rate
  • PPh3
  • Equatorial Form
  • Triphenylphosphine
  • Hydrogen Transfer