Suzuki-Miyaura coupling reaction of catalyzing aryl chloride by N-heterocyclic carbine-palladium-imidazole complex at room temperature under condition of water phase

A nitrogen-heterocyclic carbene and imidazole complex technology, applied in the field of Suzuki coupling reaction, to achieve the effects of easy preparation, low price, and low requirements for reaction conditions

Inactive Publication Date: 2011-08-17
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Therefore, the development of a nitrogen-heterocyclic carbene-metal palladium-imidazole complex that is very stable to air and water vapor as a catalyst to realize the Suzuki-Miyaura coupling reaction of aryl chlorides at room temperature is of great importance to chemists. said, remains a very big challenge

Method used

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  • Suzuki-Miyaura coupling reaction of catalyzing aryl chloride by N-heterocyclic carbine-palladium-imidazole complex at room temperature under condition of water phase
  • Suzuki-Miyaura coupling reaction of catalyzing aryl chloride by N-heterocyclic carbine-palladium-imidazole complex at room temperature under condition of water phase
  • Suzuki-Miyaura coupling reaction of catalyzing aryl chloride by N-heterocyclic carbine-palladium-imidazole complex at room temperature under condition of water phase

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0025] Synthesis of Nitrocyclic Carbene-Pd(II)-Imidazole Complexes

[0026]

[0027] Under nitrogen protection, add IPr-HCl (2.2304g, 5.2mmol), PdCl 2 (0.8863g, 5.0mmol), K 2 CO 3 (0.6931 g, 5.0 mmol), tetrahydrofuran (30.0 mL) and 1-methylimidazole (1.6 mL, 20 mmol). The reaction mixture was heated to reflux for 20h. Flash column chromatography gave Cat. (2.9534 g, 91%).

example 2

[0029] Reaction of Chlorobenzene with 4-Methoxyphenylboronic Acid

[0030]

[0031] Under nitrogen protection, 4-methoxyphenylboronic acid (91.2mg, 0.6mmol), potassium phosphate trihydrate (266.3mg, 1.0mmol), catalyst (3.2mg, 1.0mol%), water (2.0mL ), tetrahydrofuran (1.0 mL), chlorobenzene (52 μL, 0.5 mmol). The reaction mixture was stirred at room temperature for 24 hours. It was extracted with ethyl acetate, dried, filtered, and flash column chromatographed to obtain 4-methoxybiphenyl in a yield of 99%. 1 H NMR (CDCl 3 , 300MHz, TMS) δ3.79(s, 3H, OCH 3 ), 6.94(d, J=8.4Hz, 2H, Ar), 7.27(t, J=6.9Hz, 1H, Ar), 7.39(t, J=7.5Hz, 2H, Ar), 7.49-7.54(m, 4H, Ar). 13 C NMR (CDCl 3 , 75MHz, TMS) δ55.2, 114.1, 126.6, 126.7, 128.1, 128.7, 133.6, 140.7, 159.1.

example 3

[0033] Reaction of 4-Methoxychlorobenzene with Phenylboronic Acid

[0034]

[0035] Under nitrogen protection, phenylboronic acid (73.2mg, 0.6mmol), potassium phosphate trihydrate (266.4mg, 1.0mmol), catalyst (3.2mg, 1.0mol%), water (2.0mL), THF ( 1.0 mL), 4-methoxychlorobenzene (62 μL, 0.5 mmol). The reaction mixture was stirred at room temperature for 24 hours. Then it was extracted with ethyl acetate, dried, filtered, and flash column chromatographed to obtain 4-methoxybiphenyl in a yield of 93%. 1 H NMR (CDCl 3 , 300MHz, TMS) δ3.79(s, 3H, OCH 3 ), 6.94(d, J=8.4Hz, 2H, Ar), 7.27(t, J=6.9Hz, 1H, Ar), 7.39(t, J=7.5Hz, 2H, Ar), 7.49-7.54(m, 4H, Ar). 13 C NMR (CDCl 3 , 75MHz, TMS) δ55.2, 114.1, 126.6, 126.7, 128.1, 128.7, 133.6, 140.7, 159.1.

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Abstract

The invention provides a reaction method which is as follows: starting from simple and available imidazole salts, corresponding N-heterocyclic carbine-metal-imidazole complexes are synthesized; and then a Suzuki-Miyaura coupling reaction of aryl or heteroaryl boronic acid and aryl chloride by utilizing the complexes at room temperature under the condition of a water phase is carried out. The centers of metals related in the metal salts in the invention can be iron, copper, silver, nickel, palladium, cobalt, rhodium, ruthenium and the like. A catalyst used in the invention is easy to prepare, can be quantitatively synthesized and is stable to air and moisture. By using the catalyst, the corresponding coupling reaction is achieved under the condition that catalytic amount is only 0.01%, and yield is excellent. Compared with other systems reported in documents, the catalytic system is cheap in price, reaction is easy to operate and can be smoothly carried out at room temperature, and the requirement on reaction conditions is extremely low, thus the catalytic system has a good industrial application prospect.

Description

technical field [0001] The present invention relates to a class of nitrogen heterocyclic carbene-palladium-imidazole complex derived from a large hindered amine compound as a catalyst, the Suzuki ( Suzuki-Miyaura) coupling reaction. Through this method, the Suzuki coupling reaction of cheap and easily available aryl chlorides can be realized at room temperature, and a series of biaryl or biheteroaryl compounds can be synthesized. Background technique [0002] Coupling reactions catalyzed by transition metal palladium are a general method for forming carbon-carbon bonds [a) A. de Meijere, F. Diederich, Metal-catalyzed cross-coupling reactions; 2 nd Ed.; Wiley: New York, 2004; b) E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis; Wiley: New York, 2002]. Among these approaches, reactions with nitrogen heterocyclic carbene ligands have attracted much attention from chemists in the past few years [a) W.A. Herrmann, Angew. Chem. Int. Ed. 2002, 41, 1290; b)...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00C07F15/02C07F1/08C07F1/10C07F15/04C07F15/06B01J31/22C07B37/00C07C41/30C07C43/205C07C43/225C07C45/68C07C47/23C07C49/782C07C201/12C07C205/06C07D307/42C07D213/30
Inventor 邵黎雄陆建梅唐义强
Owner WENZHOU UNIVERSITY
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