Palladium-Catalyzed α-Arylation of Carbonyl Compounds and Nitriles
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- 23 January 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 36 (4) , 234-245
- https://doi.org/10.1021/ar0201106
Abstract
The palladium-catalyzed α-arylation of ketones has become a useful and general synthetic method. In this process, an enolate is generated from a ketone and base in the presence of an aryl halide, and a palladium catalyst couples this enolate with the aryl halide. With the advent of new catalysts composed of sterically hindered, electron-rich alkylphosphine and N-heterocyclic carbene ligands, this process now encompasses a broad range of enolates and related anions, including those derived from amides, esters, aldehydes, nitriles, malonates, cyanoesters, nitroalkanes, sulfones, and lactones. In the proposed mechanism for this reaction, the carbon−carbon bond of the product is formed by reductive elimination from an arylpalladium enolate intermediate. The structures and reactions of arylpalladium complexes of enolate, cyanoalkyl, and malonate ions have been studied to determine how the binding mode and electronic and steric parameters influence the rate and mechanism of reductive elimination.Keywords
This publication has 44 references indexed in Scilit:
- Metal‐Catalyzed Cross‐Coupling ReactionsPublished by Wiley ,1998
- Palladium-Catalyzed Direct α-Arylation of Ketones. Rate Acceleration by Sterically Hindered Chelating Ligands and Reductive Elimination from a Transition Metal Enolate ComplexJournal of the American Chemical Society, 1997
- Asymmetric synthesis of alkyl 2-arylalkanoates by cross-coupling reactions cabled by Pd complexesJournal of Molecular Catalysis, 1992
- Synthesis and reactions of nickel and palladium carbon-bound enolate complexesOrganometallics, 1990
- Equilibrium acidities in dimethyl sulfoxide solutionAccounts of Chemical Research, 1988
- Variety in the coordination modes of β-dicarbonyl compounds in metal complexesCoordination Chemistry Reviews, 1986
- Reactive enolates from enol silyl ethersAccounts of Chemical Research, 1985
- Arylation and 1-Alkenylation on α-Position of Ketones via Tributyltin Enolates Catalyzed by Palladium ComplexBulletin of the Chemical Society of Japan, 1984
- Catalysis of the arylation of the reformatsky reagent by palladium or nickel complexes. Synthesis of aryl acid estersJournal of Organometallic Chemistry, 1979
- A nickel catalyst for the arylation and vinylation of lithium ester enolatesJournal of the American Chemical Society, 1977