Jiayi Xu

Palladium-Catalyzed Asymmetric Allylic Alkylation of 2-Acylimidazoles as Ester Enolate Equivalents

A broad range of highly enantioenriched 2-acylimidazoles are synthesized by palladium-catalyzed decarboxylative asymmetric allylic alkylation (DAAA) of 2-imidazolo-substituted enol carbonates. The enantioenriched 2-acylimidazole products can easily be converted to the corresponding carboxylic acid, ester, amide, and ketone derivatives with complete retention of the enantiopurity. The synthetic utility of this new method is demonstrated in the short, efficient synthesis of cetiedil.

Ligand Controlled Highly Regio- and Enantioselective Synthesis of α-Acyloxyketones by Palladium-Catalyzed Allylic Alkylation of 1,2-Enediol Carbonates

The palladium catalyzed decarboxylative asymmetric allylic alkylation of allyl 1,2-enediol carbonates 1 can decompose to either alpha-hydroxyketones 3 or alpha-hydroxyaldehydes 4. The product distribution is largely controlled by the ligand. Using Lnaph in DME we exclusively obtained the ketone product in good to excellent yields and high enantiomeric excesses. The reaction proceeds under extremely mild conditions, so we can have a broad range of choices of OR. Besides the commonly used protection groups such as OAc and OPiv, a more functionalized group such as methyl but-2-enoyl group can also be used, downstream process of which can afford other synthetically interesting structures.

Palladium‐Catalyzed Allylic Alkylation of Carboxylic Acid Derivatives: N‐Acyloxazolinones as Ester Enolate Equivalents

A general asymmetric allylic alkylation of ester enolate equivalents at the carboxylic acid oxidation state is reported. N-Acylbenzoxazolinone-derived enol carbonates are synthesized in good yield and employed in the palladium-catalyzed alkylation reaction. Good yields (up to 99%) and enantioselectivities (up to 99% ee) are obtained and the imide products are readily converted to a series of carboxylic acid derivatives without loss of enantiopurity. High enantioselectivity in the reaction is achieved by a new strategy for ligand design involving variation of the steric properties of the diarylphosphine moiety.