Modern Palladium Catalysis

Bimetallic redox synergy in oxidative palladium catalysis.

Polynuclear transition metal complexes, which are embedded in the active sites of many metalloenzymes, are responsible for effecting a diverse array of oxidation reactions in nature. The range of chemical transformations remains unparalleled in the laboratory. With few noteworthy exceptions, chemists have primarily focused on mononuclear transition metal complexes in developing homogeneous cata...

Concepts of Modern Catalysis and Kinetics

Arylboration of alkenes by cooperative palladium/copper catalysis.

Arylboration of vinylarenes and methyl crotonate with aryl halides and bis(pinacolato)diboron by cooperative Pd/Cu catalysis has been developed, giving 2-boryl-1,1-diarylethanes and an α-aryl-β-boryl ester in a regioselective manner. The reaction is compatible with a variety of functionalities and amenable to be scaled-up to a gram scale with no detriment to the yield. A short synthesis of the ...

High-oxidation-state palladium catalysis: new reactivity for organic synthesis.

Recent years have seen the rapid development of a new field of palladium catalysis in organic synthesis. This chemistry takes place outside the usually encountered Pd(0)/Pd(II) cycles. It is characterized by the presence of strong oxidants, which prevent further palladium(II)-promoted reactions at a given point of the catalytic cycle by selective metal oxidation. The resulting higher-oxidation-...

Ion-paired chiral ligands for asymmetric palladium catalysis.

Conventional chiral ligands rely on the use of a covalently constructed, single chiral molecule embedded with coordinative functional groups. Here, we report a new strategy for the design of a chiral ligand for asymmetric transition-metal catalysis; our approach is based on the development of an achiral cationic ammonium-phosphine hybrid ligand paired with a chiral binaphtholate anion. This ion...