A new generation of air stable, highly active Pd complexes for C-C and C-N coupling reactions with aryl chlorides

Angewandte Chemie - International Edition

Volumn 41, Issue 19, 2002, Pages 3668-3671

  Schnyder, Anita ^b   Indolese, Adriano F ^a   Studer, Martin ^b   Blaser, Hans Ulrich ^b  

^a Rohner AG   (Switzerland)

^b SOLVIAS AG   (Switzerland)

Author keywords

Aryl chlorides; Coupling reactions; Homogeneous catalysis; Palladacyles; Phosphanes

Indexed keywords

CATALYSIS; CATALYSTS; OPTIMIZATION; PALLADIUM;

COUPLING REACTIONS;

CHLORINE COMPOUNDS;

BROMINE DERIVATIVE; CARBON; CHLORIDE; IODIDE; NITROGEN; PALLADIUM COMPLEX;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; COMPLEX FORMATION; MOLECULAR STABILITY;

EID: 0037020372     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20021004)41:19<3668::AID-ANIE3668>3.0.CO;2-U     Document Type: Article

References (35)

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8. Heck reaction: a) N. J. Whitcombe, K. K. Hii. S. E. Gibson. Tetrahedron 2001, 57, 7449; b) I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000. 100, 3009; c) R. Stürmer, Angew. Chem. 1999, 111, 3509; Angew. Chem. Int. Ed. 1999, 38. 3307; Suzuki coupling: d) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2475; e) G. Y. Li, G. Zheng, A. F. Noonan, J. Org. Chem. 2001, 66, 8677. and references therein; f) N. Miyaura in Advances in Metal-Organic Chemistry. Vol. 6 (Ed.: L. S. Liebeskind). JAI, London. 1998, p. 187: Buchwald-Hartwig amination: g) J. P. Wolfe, H. Tomori, J. P. Sadighi, J. Yin, S. L. Buchwald, J. Org. Chem. 2000, 65, 1158; h) A. Ehrentraut, A. Zapf. M. Beller. Adv. Synth. Catal. 2002, 344, 209, and references therein.
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21. 2 was synthesized according to J. R. Goerlich, R. Schmutzler, Phosphorus Sulfur Silicon Relat. Elem. 1995, 102, 211.
22. 4 (3 mmol) in dioxane (2 mL) were heated to 100°C. A solution of the catalyst was prepared by mixing the palladacycle (0.01 mmol Pd) with a solution of the ligand (0.015 mmol) in dioxane (0.2 mL), and it was added to the hot reaction mixture. The reaction mixture was stirred for 20 h. Samples were withdrawn by syringe and analyzed by GLC. Heck reaction: Sodium carbonate (7.5 mmol) was placed in a Schlenk tube under argon. Degassed N.N-dimethylacetamide (DMAc, 4 mL), 4-chlorotoluene (5 mmol), butyl acrylate (7.5 mmol), and diethylene glycol dibutyl ether (internal standard) were added, and the reaction mixture was heated to 140°C. A solution of the catalyst 1 (0.1 mmol) in DMAc (1 mL) was added by syringe to the hot reaction mixture. The reaction mixture was stirred for 20 h. After cooling the reaction mixture to room temperature, it was partitioned between diethyl ether and water, and the organic phase was analyzed by GLC. Arylation reaction: NaOtBu (3.9 mmol) was placed in a Schlenk tube under argon. Degassed toluene (3 mL), 4-chlorotoluene (3 mmol), and propiophenone (3.6 mmol) were added, and the reaction mixture was stirred for 30 minutes at room temperature. It was then heated to 110°C, and a solution of the catalyst 1 (0.06 mmol) in toluene (1 mL) was added by syringe to the hot reaction mixture. The reaction mixture was stirred for 15 h. After cooling the reaction mixture to room temperature, it was partitioned between tert-butyl methyl ether (TBME) and water, and the organic phase was analyzed by GLC. Amination reactions: NaOtBu (4.2 mmol) was placed in a Schlenk tube under argon. Degassed toluene (3 mL), aryl chloride (3 mmol), and amine (3.6 mmol) were added, and the reaction mixture was stirred for 30 min at room temperature. It was then heated to 110°C. and a solution of the catalyst 1 (0.06 mmol) in toluene (1 mL) was added by syringe to the hot reaction mixture. The reaction mixture was stirred for 15 h. After cooling the reaction mixture to room temperature, it was partitioned between TBME and water, and the organic phase was analyzed by GLC.
23. A. F. Littke, G. C. Fu, Angew. Chem. 1998, 110, 3586; Angew. Chem. Int. Ed. 1998, 37, 3387; A. F. Littke, G. C. Fu, J. Org. Chem. 1999, 64, 10.
24. A. F. Littke, G. C. Fu, Angew. Chem. 1998, 110, 3586; Angew. Chem. Int. Ed. 1998, 37, 3387; A. F. Littke, G. C. Fu, J. Org. Chem. 1999, 64, 10.
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26. General procedure: Complexes 9-12 were easily prepared by adding the appropriate phosphane to a degassed suspension of the dimeric palladacyclic chloride 8 in dichloromethane under argon. The resulting complexes are soluble and the solutions are stable against hydrolysis and oxidation by air. Some metallic palladium was removed by filtering the solution through a plug of silica. The solutions were concentrated to a minimal volume and the complexes precipitated with hexane. Complexes 9-12 were obtained as yellow to brownish yellow powders in medium to high yields that were completely odorless and air stable for at least several months. (For details see the Supporting Information).
27. [7], was not stable and could not be isolated.
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34. A. Indolese, Solvias, unpublished results.
35. This complex is commercially available in laboratory quantities from Strem and in technical quantities from Solvias AG.