Rauhut-Currier reaction

What is Rauhut-Currier reaction?

In 1963, Rauhut and Currier reported a phosphine-catalyzed dimerization of electron-deficient alkenes, which is commonly known as the Rauhut-Currier reaction or Rauhut-Currier dimerization.

Rauhut-Currier reaction - general reaction scheme - Rauhut-Currier dimerization
Rauhut-Currier reaction
  • R1 = H, alkyl, aryl
  • R’ = alkyl, aryl
  • X = CN, COOEt, COOMe, SO2R, NO2, etc. (see list of acronyms)

Rauhut-Currier reaction has relatively low selectivity and yield. However, the dimerization of methyl acrylate at temperatures ranging from 50 to 110°C always results in head-to-tail dimer, and the intramolecular dimerization of unsymmetrical bis(enones) with enough steric or electronic bias produces single products.

Furthermore, when ethyl acrylate and acrynitrile are reacted in t-butanol at 100 °C in the presence of tributylphosphine, 48 % of only one type of cross-condensation product is obtained along with self-dimerization products.

However, acrynitrile polymerizes vigorously under the Rauhut-Currier reaction conditions at refluxing temperatures. Nonetheless, the dimer and trimer of acrynitrile can still be obtained if the reaction is carried out in acetonitrile by adding an additional proton donor, such as water or t-butanol, and separating tributylphosphine before isolating the product.

References

Rauhut, M. and Currier, H., (American Cyanamide Co.), “Preparation of dialkyl 2-methyleneglutarates” U.S. Patent, 1963, US 3074999

Shares