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The influence of steric effects on the regio- and stereospecificity of the addition of thiolates to tert-butylacetylene in a proton-donating medium

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

Conclusions

  1. 1.

    A method which fully eliminates the competing free-radical reaction was developed for the nucleophilic addition of thiols to alkylacetylenes.

  2. 2.

    Under purely nucleophilic conditions steric effects substantially affect the regioorieatatioa of a thiolate ion adding to tert-butylacetylene. The proportion of attack at theβ atom, of the C ≡ C bond increases with increase in the volume of the nucleophilic reagent.

  3. 3.

    Theβ adducts are formed strictly stereospecifically by a nucleophilic mechanism, of 1,2-anti-addition, and steric effects do not affect the stereochemistry of the process.

  4. 4.

    It was found that the ratio of the regioisomers formed in the reaction of 1-alkynes with thiols and alcohols correlates well with Charton' s steric constants for alkyl groups in the nucleophilic reagent.

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Literature cited

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Authors and Affiliations

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

    V. A. Laba, A. V. Sviridova, A. A. Kron & E. N. Prilezhaeva

Authors
  1. V. A. Laba
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  2. A. V. Sviridova
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  3. A. A. Kron
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  4. E. N. Prilezhaeva
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Additional information

For the preliminary Communication, see [1].

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1566–1573, July, 1977.

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Laba, V.A., Sviridova, A.V., Kron, A.A. et al. The influence of steric effects on the regio- and stereospecificity of the addition of thiolates to tert-butylacetylene in a proton-donating medium. Russ Chem Bull 26, 1438–1444 (1977). https://doi.org/10.1007/BF00928524

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  • DOI: https://doi.org/10.1007/BF00928524

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