Baylis-Hillman reaction¹ has recently become an important method for carbon-carbon bond formation. It involves tertiary amine catalyzed coupling of an acrylate and an aldehyde or ketone to produce a highly functional acrylate that can be used as an intermediate in a synthetic sequence. While DABCO (1,4-diazabicyclo[2.2.2]octane) has often been the catalyst of choice, DMAP has been found to be a very effective catalyst for the hydroxymethylation of 2-cyclohexanones, whereas when DABCO was used as the intended catalyst only starting materials were returned.²

Racemization: A series of chiral α-substituted carboxylic acids have been found to react without racemization  with sensitive α-functionalized isocyanates at 0^oC in dichloromethane with a catalytic amount of DMAP present to form amides in high yield.³

Dakin-West Scale-up: A pyrrolopyrimidine was required in 100 Kg quantities for pharmaceutical development.  This required preparation of an acetylaminobutanone intermediate which could be obtained easily in the laboratory by trea®ent of alanine with acetic anhydride and pyridine – the Dakin-West procedure.⁴ However, this procedure could not be used safely on a technical scale because of the sudden evolution of a stoichiometric amount of carbon dioxide in the decarboxylation step.  The chemists at Novartis AG developed a procedure that utilized DMAP and TEA⁵ with additional acetic acid to provide water to promote azlactone hydrolysis and facilitate decarboxylation. Alanine was added as the limiting reagent to control carbon dioxide evolution.  The result was formation of acetylaminobutanone safely (50 Kg in a 400 L reactor) in greater than 90% yield, with great reduction in the amount of acetic anhydride used.⁶