New Ligands for a General Palladium‐Catalyzed Amination of Aryl and Heteroaryl Chlorides
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- 15 June 2004
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 10 (12), 2983-2990
- https://doi.org/10.1002/chem.200306026
Abstract
The synthesis and application of monodentate N-substituted heteroarylphosphines is described. In general, the ligands are conveniently prepared by selective metallation at the 2-position of the respective N-substituted heterocycle (pyrrole, indole) by using n-butyllithium/tetramethylethylenediamine (TMEDA) followed by quenching with dialkyl- or diarylchlorophosphines. Of the different ligands prepared, the new dialkyl-2-(N-arylindolyl)phosphines (cataCXium® P) perform excellently in the palladium-catalyzed amination of aryl and heteroaryl chlorides. Coupling of both activated and deactivated chloroarenes proceeds under mild conditions (room temperature to 60 °C). By using optimized conditions remarkable catalyst productivity (total turnover number, TON, up to 8000) and activity (turnover frequency, TOF=14 000 h−1 at 75 % conversion) are observed.Keywords
This publication has 63 references indexed in Scilit:
- Comparison of palladium carbene and palladium phosphine catalysts for catalytic coupling reactions of aryl halidesJournal of Molecular Catalysis A: Chemical, 2004
- Application of a New Bicyclic Triaminophosphine Ligand in Pd-Catalyzed Buchwald−Hartwig Amination Reactions of Aryl Chlorides, Bromides, and IodidesThe Journal of Organic Chemistry, 2003
- A Versatile Catalyst for the Sonogashira Coupling of Aryl ChloridesAngewandte Chemie, 2003
- Unparalleled Rates for the Activation of Aryl Chlorides and Bromides: Coupling with Amines and Boronic Acids in Minutes at Room TemperatureAngewandte Chemie, 2002
- Efficient Synthesis of Fine Chemicals and Organic Building Blocks Applying Palladium-Catalyzed Coupling ReactionsChemical Engineering & Technology, 2001
- Efficient Synthesis of Well-Defined, High Molecular Weight, and Processible Polyanilines under Mild Conditions via Palladium-Catalyzed AminationJournal of the American Chemical Society, 2000
- Mechanistic Studies of the Palladium-Catalyzed Amination of Aryl Halides and the Oxidative Addition of Aryl Bromides to Pd(BINAP)2 and Pd(DPPF)2: An Unusual Case of Zero-Order Kinetic Behavior and Product InhibitionJournal of the American Chemical Society, 2000
- Synthesis and nuclear magnetic resonance spectroscopic studies of 1‐arylpyrrolesJournal of Heterocyclic Chemistry, 2000
- Synthesis, Structure, and Reactivity of a Palladium Hydrazonato Complex: A New Type of Reductive Elimination Reaction To Form C−N Bonds and Catalytic Arylation of Benzophenone HydrazoneAngewandte Chemie, 1998
- Palladacyclen als effiziente Katalysatoren für ArylkupplungsreaktionenAngewandte Chemie, 1995