Rauhut–Currier reaction

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The Rauhut–Currier reaction, also called the

catalyst.[3] 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. In comparison to the MBH reaction, the RC reaction lacks substrate reactivity and regioselectivity
.

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

Rauhut–Currier reaction
Rauhut–Currier reaction

This reaction was also found to work for acrylonitrile.

RC cross-couplings are known but suffer from lack of selectivity. Amines such as DABCO can also act as catalyst. The reactivity is improved in intramolecular RC reactions, for example in the isomerization of di-enones to form cyclopentenes:[4]

Intramolecular Rauhut–Currier reaction
Intramolecular Rauhut–Currier reaction

A similar reaction by

protected cysteine and potassium tert-butoxide afforded a cyclohexene with 95% enantiomeric excess:[5]

Enantioselective Rauhut–Currier reaction
Enantioselective Rauhut–Currier reaction

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

References

  1. doi:10.1021/ja017123j
  2. ^ Preparation of dialkyl-2-methylene glutamates Rauhut, M. M.; Currier, H. U.S. Patent 3074999 1963 January 22, American Cyanamid Co., 1963. U.S. patent 3,074,999
  3. doi:10.1016/j.tet.2009.02.066
  4. ^ 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
    doi:10.1021/ja0121686
  5. doi:10.1021/ja067139f
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