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Method for preparing asymmetric substituted aryl compound or terphenyl derivative by one-pot tandem reaction of functionalized imidazole salt and palladium salt

A series reaction, aryl dihalide technology, applied in the field of one-pot series reaction catalyzed by functionalized imidazolium salt and palladium salt to prepare asymmetric substituted aryl compounds or terphenyl derivatives, can solve the problem of less application research and the like

Inactive Publication Date: 2010-02-17
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the commonly used N-heterocyclic carbene ligands are mostly simply substituted imidazolium salts, and functionalized imidazolium salt ligands can significantly enhance the stability of catalysts and improve catalytic efficiency, but relatively few studies have been conducted on the application of such ligands.

Method used

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  • Method for preparing asymmetric substituted aryl compound or terphenyl derivative by one-pot tandem reaction of functionalized imidazole salt and palladium salt
  • Method for preparing asymmetric substituted aryl compound or terphenyl derivative by one-pot tandem reaction of functionalized imidazole salt and palladium salt
  • Method for preparing asymmetric substituted aryl compound or terphenyl derivative by one-pot tandem reaction of functionalized imidazole salt and palladium salt

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0126] Preparation of (E)-butyl 3-(biphenyl-4-yl)acrylate. The reaction formula is as follows:

[0127]

[0128] The specific preparation method is: add 4-bromoiodobenzene (282mg, 1.0mmol), 5mL DMF solvent, L·HCl (6mg, 2.0mol%), Pd(OAc) in the Schlenk reaction tube successively 2 (2 mg, 1.0 mol%), NaOAc (100 mg, 1.2 mmol), n-butyl acrylate (134 mg, 1.05 mmol). Then the reaction solution was heated to 120° C. for 2 hours and then cooled to room temperature. Phenylboronic acid (183 mg, 1.5 mmol) and Cs were added directly 2 CO 3 (400mg, 1.2mmol) and continue to heat up to 80°C for 3 hours. After the reaction solution was cooled to room temperature, it was poured into 20 mL of water, and the 2 Cl 2 (3 x 20 mL) extraction. The combined organic layers were washed with water (2×20 mL) and washed with anhydrous MgSO 4 After drying, the solvent was evaporated under reduced pressure, and the residue was separated by column chromatography (ethyl acetate / petroleum ether=5 / 95) ...

Embodiment 2

[0130] Preparation of (E)-ethyl 3-(4'-chlorob iphenyl-4-yl)acrylate. The reaction formula is as follows:

[0131]

[0132] The specific preparation method is: add 4-bromoiodobenzene (282mg, 1.0mmol), 5mL DMAc solvent, L HCl (6mg, 2.0mol%), Pd(OAc) in the Schlenk reaction tube successively 2 (2 mg, 1.0 mol%), NaOAc (100 mg, 1.2 mmol), ethyl acrylate (105 mg, 1.05 mmol). Then the reaction solution was heated to 120° C. for 1 hour and then cooled to room temperature. 4-Chlorophenylboronic acid (234 mg, 1.5 mmol) and Cs were added directly 2 CO 3 (400mg, 1.2mmol) and continue to heat up to 80°C for 3 hours. After the reaction solution was cooled to room temperature, it was poured into 20 mL of water, and the 2 Cl 2 (3 x 20 mL) extraction. The combined organic layers were washed with water (2×20 mL) and washed with anhydrous MgSO 4 After drying, the solvent was evaporated under reduced pressure, and the residue was separated by column chromatography (ethyl acetate / petrol...

Embodiment 3

[0134]Preparation of (E)-butyl 3-(4'-chlorobiphenyl-3-yl)acrylate. The reaction formula is as follows:

[0135]

[0136] The specific preparation method is: add 3-bromoiodobenzene (282mg, 1.0mmol), 5mL DMF solvent, L·HCl (3mg, 1.0mol%), Pd(OAc) in the Schlenk reaction tube successively 2 (4 mg, 2.0 mol%), NaOAc (162 mg, 2.0 mmol), n-butyl acrylate (134 mg, 1.05 mmol). Then the reaction solution was heated to 120° C. for 2 hours and then cooled to room temperature. 4-Chlorophenylboronic acid (234 mg, 1.5 mmol) and Cs were added directly 2 CO 3 (400mg, 1.2mmol) and continue to heat up to 80°C for 3 hours. After the reaction solution was cooled to room temperature, it was poured into 20 mL of water, and the 2 Cl 2 (3 x 20 mL) extraction. The combined organic layers were washed with water (2×20 mL) and washed with anhydrous MgSO 4 After drying, the solvent was evaporated under reduced pressure, and the residue was separated by column chromatography (ethyl acetate / petrol...

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Abstract

The invention discloses a catalyst and a method for preparing an asymmetric substituted aryl compound or a terphenyl derivative by a one-pot tandem reaction under the catalysis of functionalized imidazole salt and palladium salt. The catalyst mainly comprises the functionalized imidazole salt and the palladium salt in a ratio of 1:2 to 6:1. The method comprises the following steps: using the catalyst to respectively carry out one-pot tandem reactions between Heck / Suzuki, Heck / Heck, and Heck / Sonagashira by using aryl halides or a derivative thereof as a substrate in organic solvent; and directly preparing the asymmetric substituted aryl compound because intermediate products need not to be separated. A prepared chlorinated biphenyl compound can also carry out a Suzuki or Buchwald-Hartwig reaction for preparing the terphenyl derivative and an amino biphenyl compound. The catalyst has simple preparation and extremely low consumption and can catalyze more than two different coupling reactions, thereby having high efficiency and low cost; and the one-pot tandem reaction method has simple and convenient operation and mild conditions, avoids pollution, reduces waste, obtains high-yield valuable products and can be widely applied to the fine chemistry industry, the pharmaceuticals industry, and the like.

Description

Technical field: [0001] The present invention relates to a method for preparing asymmetric substituted aryl compounds and terphenyl derivatives by one-pot series reaction of aryl dihalides or derivatives thereof. Background technique: [0002] Asymmetrically substituted aryl compounds, biphenyl derivatives, terphenyl derivatives and aminobiphenyl derivatives have important applications in the preparation of natural products, pharmaceutical intermediates and materials science. However, the known methods for preparing such compounds are cumbersome, generally require multi-step separation and purification operations, and require the use of expensive and environmentally harmful phosphine ligand catalysts, which limits their industrial application. In recent years, as the supplement and replacement of phosphine ligands, cheap and easy-to-obtain N-heterocyclic carbene ligands have been widely used in catalytic reactions, especially in carbon-carbon and carbon-heteroatom coupling r...

Claims

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Application Information

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IPC IPC(8): B01J31/30B01J31/04B01J31/02C07B61/00C07C67/343C07C69/618C07C69/65C07C69/734C07C25/24C07C17/26C07C67/313C07C2/86C07C15/54C07C255/57C07C253/30C07D295/033C07D295/023C07C211/55C07C209/10
Inventor 陈万芝张效铭
Owner ZHEJIANG UNIV
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