Galat reactions between
aldehydes and substituted malonic acids
half oxyester were found to be efficiently catalyzed by morpholine
in refluxing toluene. This transformation allows the stereoselective
synthesis of diverse α,β-disubstituted acrylates in moderate
to good yields. This method constitutes an attractive alternative
to existing methods in terms of scope and eco-compatibility.
The decarboxylative Mannich reaction between imines and substituted malonic acids half-oxyesters (SMAHOs) has been developed using 1,4-diazabicyclo[2.2.2]octane (DABCO) as an organocatalyst. The reaction proceeds under simple reaction conditions and tolerates a broad range of substrates, affording general access to β 2,3 -aminoesters, the syn diastereomer being the major one. An alternative multicomponent protocol has also been developed to increase the overall eco-compatibility of the process.
Multicomponent Mannich reactions through C−H bond activation are described. These transformations allowed for the straightforward generation of densely substituted benzylic and homo‐benzylic amines in good yields. The reaction involves a reaction between two transient species: an organometallic species, generated by transition‐metal‐catalyzed sp2 or sp3 C−H bond activation and an in situ generated imine. The use of an acetal as an aldehyde surrogate was found essential for the reaction to proceed. The process could be successfully applied to RhIII‐catalyzed sp2 C−H bond functionalization and extended to CuII‐catalyzed sp3 C−H bond functionalization.
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