Extracurricular laboratory:new discovery of Tris(dibenzylideneacetone)dipalladium-chloroform

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A number of ethyl 2-aryl-2-formylpent-4-enoates containing acyclic, all-carbon, aryl-substituted quaternary stereocenters have been synthesized via intermolecular palladium-catalyzed asymmetric allylic alkylation (Pd-AAA). Here, a 2-aryl-3-hydroxyacrylate was used as an unprecedented nucleophilic counterpart instead of the widely used ketonic substrate. This produced a very rare, all-carbon chiral center including an easily utilized aldehyde or ketone moiety. Chiral ligand (R,R)-DACH-naphthyl Trost ligand was found to be optimal in this Pd-AAA reaction and provided good to excellent yields (75-99%) and enantioselectivities (52-94%) with a range of analogues. To show the utility of this method, it was used to synthesize an all-carbon quaternary, alpha,alpha-disubstituted beta-lactone.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method