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Palladium-catalyzed alpha-arylation of carbonyl compounds and nitriles.
Acc Chem Res. 2003 Apr; 36(4):234-45.AC

Abstract

The palladium-catalyzed alpha-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.

Authors+Show Affiliations

Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.No affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, P.H.S.

Language

eng

PubMed ID

12693921

Citation

Culkin, Darcy A., and John F. Hartwig. "Palladium-catalyzed Alpha-arylation of Carbonyl Compounds and Nitriles." Accounts of Chemical Research, vol. 36, no. 4, 2003, pp. 234-45.
Culkin DA, Hartwig JF. Palladium-catalyzed alpha-arylation of carbonyl compounds and nitriles. Acc Chem Res. 2003;36(4):234-45.
Culkin, D. A., & Hartwig, J. F. (2003). Palladium-catalyzed alpha-arylation of carbonyl compounds and nitriles. Accounts of Chemical Research, 36(4), 234-45.
Culkin DA, Hartwig JF. Palladium-catalyzed Alpha-arylation of Carbonyl Compounds and Nitriles. Acc Chem Res. 2003;36(4):234-45. PubMed PMID: 12693921.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Palladium-catalyzed alpha-arylation of carbonyl compounds and nitriles. AU - Culkin,Darcy A, AU - Hartwig,John F, PY - 2003/4/16/pubmed PY - 2003/5/29/medline PY - 2003/4/16/entrez SP - 234 EP - 45 JF - Accounts of chemical research JO - Acc Chem Res VL - 36 IS - 4 N2 - The palladium-catalyzed alpha-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. SN - 0001-4842 UR - https://www.unboundmedicine.com/medline/citation/12693921/Palladium_catalyzed_alpha_arylation_of_carbonyl_compounds_and_nitriles_ L2 - https://doi.org/10.1021/ar0201106 DB - PRIME DP - Unbound Medicine ER -