Bayliss-Hillman reaction

Auge,J. Lubin, N. Lubineau, A., Acceleration in water of the Bayliss-Hillman reaction. Tetrahedron Lett. 1994, 35, 7947. 

Nazarov, I. N. Torgov, I. B. Terekhova, L. N. Bull. Acad. Sci. (USSR) 1942, 200. I. N. Nazarov (1900—1957), a Soviet Union Scientist, discovered this reaction in 1942. It was said that almost as many young synthetic chemists have been lost in the pursuit of an as)Tnmetric Nazarov cychzation as of the Bayliss—Hillman reaction. 

The Bayliss-Hillman reaction is commonly used for the coupling of Michael acceptors with aldehydes to give /3-hydroxy-a-methylene esters/ketones/nitriles. The use of imines in place of aldehydes provides entry to the corresponding /3-amino products. Examples of the asymmetric Bayliss-Hillman reaction with imines are very rare. Aggarwal and co-workers have shown that indium(III) triflate in combination with 3-hydroxyquinuclidine (3-HQD) catalyzes the reaction of enantiomerically pure N-p-toluenesulfinimine with methyl acrylate in an asymmetric Bayliss-Hillman reaction (eq 15). Higher diastereoselectivity was observed in the reaction of A-tert-butanesulfinimines, however, the yields were much poorer. ... 

While high-pressure reactions typically require specialized equipment, a Bayliss-Hillman reaction between p-bromohenzaldehyde and methyl acrylate has been induced by the pressure created as water freezes (2 kbar). The reaction is performed in a test tube placed in a water-filled sealed autoclave in a household refrigerator at -20°C. An 86% yield was obtained in this manner compared to 65% yield at 1 atm [17]. 

The reagent in Step 1, (E)-2-methyl -2-hexen-l-ol, was prepared using a modified Morita-Baylis-Hillman procedure with ethyl acrylate and l,4-diazabicyclo[2.2.2]octane. Other examples of the Bayliss-Hilman reaction are provided (1). The stereoisomer, (Z)-2-methyl-2-hexen-l-ol was used to prepare other aldol stereoisomers. The preparation of the (Z)-isomer is provided below by the author ... 

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