The important role of Tris(dibenzylideneacetone)dipalladium-chloroform

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Pd-Catalyzed Decarboxylative Asymmetric Protonation of Sterically Hindered alpha-Aryl Lactones and Dihydrocoumarins

Pd-catalyzed decarboxylative asymmetric protonation (DAP) has been developed for sterically hindered alpha-aryl lactone and dihydrocoumarin substrates. Optimization studies were conducted using delta-lactone- and dihydrocoumarin-derived alpha-aryl, beta-oxo-allyl esters with 2,4,6-trimethoxyphenyl as the aryl substituent. In the absence of a chiral P,N-ligand, (1R,2S)-(?)ephedrine, a cheap and readily available chiral proton donor, induced enantioselectivities of up to 92% ee and 88% ee with lactone and dihydrocoumarin substrates, respectively. Bulky aryl groups containing di-ortho substitutions and naphthyl groups gave the highest enantioselectivities of up to 92% and 86%, respectively. A stereochemical rationale is proposed to explain the preferred sense of asymmetric induction. (Figure presented.).

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