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Cross coupling reaction of arenesulphonate substrate and organic titanium

A cross-coupling reaction, arylsulfonic acid technology, applied in the preparation of organic compounds, organic substitution, organic chemistry, etc., can solve the problem of low activity of arylsulfonic acid esters, and achieve easy storage and large-scale synthesis. , the effect of reducing the reaction cost

Inactive Publication Date: 2015-12-16
THE HONG KONG POLYTECHNIC UNIV SHENZHEN RES INST
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  • Abstract
  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

However, the activity of aryl sulfonate substrates is very low. As far as we know, there is no example of successfully catalyzing the cross-coupling reaction of aryl sulfonate substrates with organic titanium.

Method used

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  • Cross coupling reaction of arenesulphonate substrate and organic titanium
  • Cross coupling reaction of arenesulphonate substrate and organic titanium
  • Cross coupling reaction of arenesulphonate substrate and organic titanium

Examples

Experimental program
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Effect test

Embodiment 1

[0015] Embodiment one: the coupling reaction of aryl p-toluenesulfonate and 4-methylphenisopropoxide titanium

[0016] In a 20mL Schlenk tube, add palladium acetate (0.025mmol) and phosphine ligand (palladium: phosphine ligand ratio is 5mol%: 20mol%), then add a magnetic stirring bar equipped with a polytetrafluoroethylene coating, and the system is replaced by Under nitrogen protection, 0.1 mL of freshly distilled triethylamine and 1.0 mL of dichloromethane were added, stirred and heated gently to a slight boil, and then sucked dry under reduced pressure to form a palladium complex.

[0017] Aryl p-toluenesulfonate (0.5 mmol), titanium 4-methylphenisopropoxide (2.5 mmol) and potassium phosphate (0.125 mmol) were then added under nitrogen. Finally, 1,4-dioxane solution (2.0 mL) was added, and then the Schlenk tube was placed in a preheated oil bath at 110° C. for 18 to 24 hours. After the reaction was completed, the reaction tube was cooled to room temperature, about 10 mL of...

Embodiment 2

[0021] Embodiment two: the coupling reaction of aryl p-toluenesulfonate and 4-methoxyphenylisopropoxide titanium

[0022] In a 20mL Schlenk tube, add palladium acetate (0.025mmol) and phosphine ligand (palladium: phosphine ligand ratio is 5mol%: 20mol%), then add a magnetic stirring bar equipped with a polytetrafluoroethylene coating, and the system is replaced by Under nitrogen protection, 0.1 mL of freshly distilled triethylamine and 1.0 mL of dichloromethane were added, stirred and heated gently to a slight boil, and then sucked dry under reduced pressure to form a palladium complex.

[0023] Aryl p-toluenesulfonate (0.5 mmol), titanium 4-methoxyphenisopropoxide (2.5 mmol) and potassium phosphate (0.125 mmol) were then added under nitrogen. Finally, 1,4-dioxane solution (2.0 mL) was added, and then the Schlenk tube was placed in a preheated oil bath at 110° C. for 18 to 24 hours. After the reaction was completed, the reaction tube was cooled to room temperature, about 10 m...

Embodiment 3

[0027] Embodiment three: the coupling reaction of heterocyclic aryl p-toluenesulfonate and organic titanium

[0028] In a 20mL Schlenk tube, add palladium acetate (0.025mmol) and phosphine ligand (palladium: phosphine ligand ratio is 5mol%: 20mol%), then add a magnetic stirring bar equipped with a polytetrafluoroethylene coating, and the system is replaced by Under nitrogen protection, 0.1 mL of freshly distilled triethylamine and 1.0 mL of dichloromethane were added, stirred and heated gently to a slight boil, and then sucked dry under reduced pressure to form a palladium complex.

[0029] Heterocyclic aryl p-toluenesulfonate (0.5 mmol), organotitanium (2.5 mmol) and potassium phosphate (0.125 mmol) were subsequently added under nitrogen. Finally, 1,4-dioxane solution (2.0 mL) was added, and then the Schlenk tube was placed in a preheated oil bath at 110° C. for 18 to 24 hours. After the reaction was completed, the reaction tube was cooled to room temperature, about 10 mL of...

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Abstract

The invention relates to a cross coupling reaction of an arenesulphonate substrate and organic titanium. The cross coupling reaction comprises steps as follows: A), after palladium acetate and indole phosphine ligands are utilized to generate a catalyst, the arenesulphonate substrate, aryl titanium, potassium phosphate and an organic solvent are added; B), the components react for 12-24 h at the temperature of 110-130 DEG C, and a biaryl compound is obtained. Compared with the Suzuki coupling reaction, the cross coupling reaction of the arenesulphonate substrate and organic titanium has the advantages that with addition of a small amount of alkali, organic titanium can be catalyzed to have the cross coupling reaction, and the reaction cost can be reduced. Besides, organic titanium is adopted as nucleophile for reaction, and compared with a Grignard reagent required to be stored in an organic solvent in the Kumada coupling reaction, solid organic titanium is easier to apply, has high stability, can be massively synthesized and is easy to store. Compared with organic tin in the Stille cross coupling reaction, organic titanium has lower toxicity and assists in improvement of applicability of the reaction.

Description

technical field [0001] The invention relates to the cross-coupling reaction of aryl p-toluenesulfonate and organic titanium. Background technique [0002] In 2002, Hayashi's research group first used organotitanium and aryl bromide and aryl triflate for the bonding reaction to form biaryl compounds. In recent years, Gau's research group and Kwong's research group have used different palladium complexes to catalyze the coupling reaction of aryl chloride and organic titanium to synthesize various biaryl compounds. [0003] Although aryl halides can react with organic titanium to form biaryl compounds, the scope of substrates is small, and the applicability needs to be improved. Aryl sulfonate substrates are complementary substrates of aryl halides, which can effectively complement or replace aryl halides as reaction substrates in the synthetic route. Therefore, if the cross-coupling reaction between aryl sulfonate substrate and organotitanium is successfully carried out, the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/04C07C1/32C07C15/14C07C41/30C07C43/205C07C17/263C07C25/18C07D215/20C07D215/227C07D317/48C07D277/64
Inventor 李幸威苏秋铭邝福儿黄永德
Owner THE HONG KONG POLYTECHNIC UNIV SHENZHEN RES INST
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