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Regioselective reaction of alkyl diazoacetates with trimethylsilylisopropenylacetylene and chemical conversions of the resulting esters of trimethylsilylethynylmethylcyclopropane-carboxylic acid

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

Conclusions

  1. 1.

    Thermocatalytic reaction of alkyl diazoacetates with an excess of trimethylsilylisopropenylacetylene in the presence of CuSO4 at 100–110° proceeds regioselectively at the double bond only, with the formation of esters of 2-trimethylsilylethynyl-2-methylcyclopropanecarboxylic acid, hydrolysis of which with aqueous-alcoholic KOH affords, according to the temperature, 2-methyl-2-ethynylcyclopropanecarboxylic acid (above 70°) or its esters (below −5°) in an overall yield of up to 40%, calculated on isopropenylacetylene. This use of a silyl protecting group may be regarded as a general method for the synthesis of ethynylcyclopropanecarboxylic acids from enynes with terminal triple bonds.

  2. 2.

    Esters of 2-trimethylsilylethynyl-2-methylcyclopropanecarboxylic acid react in the presence of CuSO4 at 110–115° with an excess of alkyl diazoacetates at the triple bond with the formation of alkyl esters of 1-(1-methyl-2-alkoxycarbonylcyclopropyl)cyclopropene-3-carboxylic acids in yields of up to 30%. These are hydrolyzed by alkali to the unstable esters of 1-(1-methyl-2-alkoxycarbonylcyclopropyl)cyclopropene-3-carboxylic acids, isolated as their adducts with cyclopentadiene.

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Authors and Affiliations

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

    E. A. Shapiro, G. V. Lun'kova, I. E. Dolgii & O. M. Nefedov

Authors
  1. E. A. Shapiro
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  2. G. V. Lun'kova
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  3. I. E. Dolgii
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  4. O. M. Nefedov
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1316–1319, June, 1981.

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Shapiro, E.A., Lun'kova, G.V., Dolgii, I.E. et al. Regioselective reaction of alkyl diazoacetates with trimethylsilylisopropenylacetylene and chemical conversions of the resulting esters of trimethylsilylethynylmethylcyclopropane-carboxylic acid. Russ Chem Bull 30, 1047–1050 (1981). https://doi.org/10.1007/BF00950291

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  • DOI: https://doi.org/10.1007/BF00950291

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