Development of .BETA.-keto ester and malonate chemistry Palladium-catalyzed new reactions of their allylic esters

Palladium-catalyzed selective anti-Markovnikov oxidation of allylic esters.

Allylic alkylations catalyzed by palladium-bis(oxazoline) complexes derived from heteroarylidene malonate derivatives.

A series of simple heteroarylidene malonate-type bis(oxazoline) ligands 4 and 5 were applied to the palladium-catalyzed allylic alkylation reaction, and the ligand 4a bearing a phenyl group afforded excellent enantioselectivity (up to 96% ee) for the allylic alkylation product. Other substrates were also examined, giving the allylic alkylated products in high yield but with poor ee values.

Palladium Catalyzed Allylic Substitution of Acyloxypyrrolinones

Enantiomerically pure alkoxypyrrolinones have been shown to be facile building blocks for a variety of stereoselective syntheses involving Diels-Alder cycloadditions , 1,3dipolar reactions, conjugate additions, and acyliminium ion intermediates. In particular the application in the asymmetric synthesis of alkaloids based on N-acyliminium ion chemistry is of current interest. For example, (R)-1-...

Palladium-catalyzed asymmetric synthesis of allylic fluorides.

The enantioselective fluorination of readily available cyclic allylic chlorides with AgF has been accomplished using a Pd(0) catalyst and Trost bisphosphine ligand. The reactions proceed with unprecedented ease of operation for Pd-mediated nucleophilic fluorination, allowing access to highly enantioenriched cyclic allylic fluorides that bear diverse functional groups. Evidence that supports a m...

Copper-catalyzed cascade reactions of α,β-unsaturated esters with keto esters

A copper-catalyzed cascade reaction of α,β-unsaturated esters with keto esters is reported. It features a copper-catalyzed reductive aldolization followed by a lactonization. This method provides a facile approach to prepare γ-carboxymethyl-γ-lactones and δ-carboxymethyl-δ-lactones under mild reaction conditions.