Kishner cyclopropane synthesis

What is Kishner cyclopropane synthesis?

The Kishner cyclopropane synthesis, named after its discoverer Kishner (Moscow State University) in 1911, involves the decomposition of pyrazolines formed from hydrazine and α,β-unsaturated ketones or aldehydes, resulting in the preparation of cyclopropane derivatives. This reaction has also been referred to as the Kishner reactionKishner decomposition, or Kishner method.

Kishner cyclopropane synthesis - Kishner decomposition - general reaction scheme - Kishner method - Kishner reaction
Kishner cyclopropane synthesis

A modified version of the Kishner cyclopropane synthesis involves the preparation of pyrazoline intermediates from diazomethane and unsaturated carbonyl compounds such as maleic and fumaric esters, which results in the formation of an ester group in the trans position. However, using maleic anhydride or maleimide results in the formation of the corresponding pyrazoline with carbonyl groups in the cis configuration.

The stability of pyrazolines varies considerably and they can decompose into cyclopropanes at different rates. In addition, the transformation of pyrazolines into cyclopropanes can be catalyzed by a trace amount of mercuric ion.

References

  • N. M. Kishner and A, Zavadovskii, J. Russ. Phys. Chem. Soc. 43, 1132-1149 (1911)
  • N. M. Kishner, J. Russ. Phys. Chem. Soc. 44, 165 (1912)
  • N. M. Kishner, J. Russ. Phys. Chem. Soc. 44, 849 (1912)
  • N. M. Kishner, J. Russ. Phys. Chem. Soc. 45, 949 (1913)
  • N. M. Kishner, J. Russ. Phys. Chem. Soc. 45, 957 (1913)
  • N. M. Kishner, J. Russ. Phys. Chem. Soc. 45, 987 (1913)
  • N. M. Kishner and I. B. Losik, Blull. Acad. Sci. U.S.S.R., Classe Sei. Chim. 1941, 49
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