Malonic esters Michael-type addition

The decarboxylation of allyl /3-keto carboxylates generates 7r-allylpalladium enolates. Aldol condensation and Michael addition are typical reactions for metal enolates. Actually Pd enolates undergo intramolecular aldol condensation and Michael addition. When an aldehyde group is present in the allyl fi-keto ester 738, intramolecular aldol condensation takes place yielding the cyclic aldol 739 as a main product[463]. At the same time, the diketone 740 is formed as a minor product by /3-eIimination. This is Pd-catalyzed aldol condensation under neutral conditions. The reaction proceeds even in the presence of water, showing that the Pd enolate is not decomposed with water. The spiro-aldol 742 is obtained from 741. Allyl acetates with other EWGs such as allyl malonate, cyanoacetate 743, and sulfonylacetate undergo similar aldol-type cycliza-tions[464]. 

Two new series of bifunctional hydrogen-bond-donor asymmetric organocatalysts have been described, based on 2-aminoquinazol-4-(l//)-one (111a) or 3-amino-benzothiadiazine-1,1-dioxide (111b) skeletons. Both types catalyse Michael additions (e.g. nitrostyrene and diethyl malonate), hydrazinations of the a-carbon of ketones and /3-ketoesters, and isomerizations of alkyne esters to aUene esters (mainly... 

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