Palladium-Catalyzed Selective Anti-Markovnikov Oxidation of Allylic Esters

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

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...

Palladium-catalyzed allylic C-H fluorination.

The first catalytic allylic C-H fluorination reaction using a nucleophilic fluoride source is reported. Under the influence of a Pd/Cr cocatalyst system, simple olefin substrates undergo fluorination with Et3N·3HF in good yields with high branched:linear regioselectivity. The mild conditions and broad scope make this reaction a powerful alternative to established methods for the preparation of ...

Palladium-catalyzed anti-Markovnikov hydroalkylation of homoallylic alcohols bearing β-fluorines.

A palladium-catalyzed anti-Markovnikov hydroalkylation of β,β-difluorinated homoallylic alcohols with alkylzinc reagents has been developed. This method affords a wide range of synthetically useful gem-difluorinated compounds with good functional group compatibility.