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Factors which affect the direction of the reaction of nucleophilic addition of CH2XCO2Et toα,β-unsaturated aldehydes in conditions of two-phase catalysis

  • Organic Chemistry
  • Published:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    The general mechanisms of the direction of addition of CH acids of the XCH2CO2Et and BrCH(CO2Et)2 type to enals in conditions of two-phase catalysis were formulated: a) CH acids (X=CO2Et, COCH3, CN) are added to enals unsubstituted in position 3 only at the C=C bond; b) enals monosubstituted in position 3 add CH acids (X=CO2Et, COCH3) at the C=C bond and CH acids (X=CN) at the C=O bond; c) enals disubstituted at position 3 add CH acids (X=CO2Et, COCH3, CN) exclusively at the C=O bond.

  2. 2.

    Quantum-chemical calculations showed that the direction of the reaction of addition of CH acids to enals cannot be explained based on concepts concerning the competition of orbital and charge interactions.

  3. 3.

    The change in the direction of addition in methylation and chlorination of the enal is due to steric hindrances which arise when the structure of the enal is altered when the reagents converge.

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Literature cited

  1. G. V. Kryshtal', V. V. Kul'ganek, V. F. Kucherov, and L. A. Yanovskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 2808 (1978).

  2. G. V. Kryshtal', V. V. Kulganek, V. F. Kucherov, and L. A. Yanovskaya, Synthesis, 107 (1979).

  3. N. I. Shtemenko, V. F. Kucherov, and L. A. Yanovskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 1444 (1979).

  4. N. I. Shtemenko, G. V. Kryshtal', and L. A. Yanovskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 445 (1981).

  5. Z. Arnol'd, V. Kral, G. V. Kryshtal', and L. A. Yanovskaya, Izv. Akad. Nauk SSSR, Ser. Khim., 2182 (1983).

  6. J. A. Pople and G. A. Segal, J. Chem. Phys.,44, 3289 (1966).

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Authors and Affiliations

  1. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow

    G. V. Kryshtal', K. Ya. Burshtein, V. V. Kul'ganek & L. A. Yanovskaya

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  1. G. V. Kryshtal'
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  2. K. Ya. Burshtein
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  3. V. V. Kul'ganek
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  4. L. A. Yanovskaya
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Additional information

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2541–2550, November, 1984.

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Kryshtal', G.V., Burshtein, K.Y., Kul'ganek, V.V. et al. Factors which affect the direction of the reaction of nucleophilic addition of CH2XCO2Et toα,β-unsaturated aldehydes in conditions of two-phase catalysis. Russ Chem Bull 33, 2328–2334 (1984). https://doi.org/10.1007/BF00948847

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  • DOI: https://doi.org/10.1007/BF00948847

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