Morita-Baylis-Hilman reaction

NHC-catalyzed reactions are unique in organic synthesis, and very useful for the construction of carbon-carbon bonds. Great success has been made for the NHC-catalyzed benzoin condensation, Stetter reactions, and a -d Umpolung reactions in the past decades. NHC catalysis has also hnd application in many other reactions, such as umpolung of Michael acceptors, Morita-Baylis-Hilman reaction, Michael additions, redox reaction, and reactions of ketenes. With the rapid development of NHC catalysis, more reactions will surely be found, and the wide applications in organic synthesis could be expected. 

Wang and co-workers reported an enantioselective metal-organic catalyzed aerobic oxidative aza-Morita-Baylis-Hilman reaction between N-aiyl THIQs and electron-deficient olefins such as acrolein and acrylonitrile (Scheme 7.7). Under co-operative catalysis with Cu(OTf)2 and quinine, sp C-H olefination at the benzylic position of THIQs occurred to afford the... 

Scheme 43 Rh- and Ru-catalyzed Morita-Baylis-Hilman type reactions...

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 ... 

---