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.

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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