Rauhut-Currier reaction

The Rauhut-Currier reaction is an organic reaction describing the dimerization or isomerization of enones by action of an organophosphine of the type R₃P.^[1] The reaction mechanism is essentially that of the related and better known Baylis-Hillman reaction (DABCO not phosphine, carbonyl not enone) but the Rauhut-Currier reaction actually predates it by several years.

Additional recommended knowledge

Safe Weighing Range Ensures Accurate Results

Weighing the right way

Recognize and detect the effects of electrostatic charges on your balance

The original 1963 reaction described the dimerization of the ethyl ester of acrylic acid to the corresponding diester of 2-methylene-glutaric acid with tributylphosphine in acetonitrile:

The reaction type has been utilized in an intramolecular isomerization of di-enones to form cyclopentenes:^[2]

A similar reaction by asymmetric synthesis organocatalyzed by a protected cysteine and potassium tert-butoxide afforded a cyclohexene with 95% enantiomeric excess:^[3]

In this reaction the phosphine is replaced by the thiol group of cysteine but the reaction is the same.

References

^ Preparation of dialkyl-2-methylene glutamates Rauhut, M. M.; Currier, H. U.S. Patent 3074999 1963 January 22, American Cyanamid Co., 1963. Link
^ Organocatalytic Michael Cycloisomerization of Bis(enones): The Intramolecular Rauhut-Currier Reaction Long-Cheng Wang, Ana Liza Luis, Kyriacos Agapiou, Hye-Young Jang, and Michael J. Krische J. Am. Chem. Soc.; 2002; 124(11) pp 2402 - 2403; (Communication) doi:10.1021/ja0121686
^ Enantioselective Rauhut-Currier Reactions Promoted by Protected Cysteine Carrie E. Aroyan and Scott J. Miller J. Am. Chem. Soc.; 2007; 129(2) pp 256 - 257; (Communication) doi:10.1021/ja067139f