Dieckmann condensation

What is Dieckmann condensation?

Dieckmann first reported a chemical reaction in 1894, which is commonly known as the Dieckmann condensation, Dieckmann reaction, or Dieckmann cyclization. This reaction involves the base-promoted intramolecular condensation of α,ω-diesters to form cyclic β-ketoesters, which can be further converted into cyclic ketones by hydrolysis and decarboxylation. The reaction is not only useful for preparing 5- or 6-membered cyclic β-ketoesters but also larger cyclic ketones, such as 10-, 16-, and 20-membered cyclic aminoketones and diaminodiketones.

Dieckmann condensation - general reaction scheme - Dieckmann reaction - Dieckmann cyclization
Dieckmann condensation

The reaction conditions and solvents vary depending on the desired product. The Dieckmann reaction is often used in tandem reactions, such as the [2+2] cycloaddition-Dieckmann condensation and conjugate addition-Dieckmann condensation. The mechanism of the Dieckmann condensation is similar to that of the Claisen condensation, and the reaction can occur in both solution and gas phases. However, the actual intermediate for condensation differs between the two phases.

References

  • Dieckmann, W. (1894), Zur Kenntniss der Ringbildung aus Kohlenstoffketten. [On the knowledge of ring formation from carbon chains.] Ber. Dtsch. Chem. Ges., 27: 102-103. https://doi.org/10.1002/cber.18940270126
  • Dieckmann, W. (1894), Ueber ein ringförmiges Analogon des Ketipinsäureesters. [On a ring analogue of the ketipic acid ester.] Ber. Dtsch. Chem. Ges., 27: 965-966. https://doi.org/10.1002/cber.189402701202
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