Preparation method of high-sterically-hindered arylborate compound

An aryl boronate and compound technology, which is applied in the field of preparation of high sterically hindered aryl boronate compounds, can solve the problems of inapplicability of aryl chlorides and the like, and achieve the expansion of the scope of the substrate, the stability of the substrate, and the reaction conditions. mild effect

Inactive Publication Date: 2015-02-04
THE HONG KONG POLYTECHNIC UNIV SHENZHEN RES INST
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Subsequently, Deng et al reported that complexes of monodentate phosphine ligands and palladium precursors can be applie...

Method used

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  • Preparation method of high-sterically-hindered arylborate compound
  • Preparation method of high-sterically-hindered arylborate compound
  • Preparation method of high-sterically-hindered arylborate compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Example 1: Synthesis of 2,6-dimethylphenylboronic acid neopentane glycol ester

[0018] In a 20 mL Schlenk tube, add tris(dibenzylideneacetone) dipalladium (0.0046 g, 0.005 mmol) and phosphine ligand (the ratio of palladium:phosphine ligand is 0.5mol%:4mol%), and then add poly Tetrafluoroethylene-coated magnetic stirring bar, the system was replaced by nitrogen protection, 0.5 mL of freshly distilled 1,4-dioxane was added, and stirred evenly for 10 minutes while adding to form a palladium complex. 2,6-Dimethylchlorobenzene (0.5 mmol), neopentyl glycol diboronate (0.6 mmol) and cesium acetate (1.5 mmol) were subsequently added under nitrogen. Finally 1,4-dioxane solution (1 mL) was added and stirring was continued for 5 minutes at room temperature. Then place the Schlenk tube in a preheated 110°C oil bath for 24 hours. After the reaction was completed, the reaction tube was cooled to room temperature, and after the consumption of the aryl chloride was detected by thin ...

Embodiment 2

[0023] Example 2: Synthesis of 2,4,6-triethylphenylboronic acid neopentyl glycol ester

[0024] In a 20 mL Schlenk tube, add tris(dibenzylideneacetone) dipalladium (0.0046 g, 0.005 mmol) and ligand (palladium:ligand ratio is 1mol%:8mol%), and then add polytetrafluoroethylene Coated magnetic stirring bar, the system was replaced by nitrogen protection, 0.5mL of freshly distilled 1,4-dioxane was added, and stirred evenly for 10 minutes while adding to form a palladium complex. 2,4,6-Triethylchlorobenzene (0.5 mmol), neopentyl glycol diboronate (0.6 mmol) and cesium acetate (1.5 mmol) were then added under nitrogen. Finally 1,4-dioxane solution (1 mL) was added and stirring was continued for 5 minutes at room temperature. Then place the Schlenk tube in a preheated oil bath at 110°C for 24 hours. After the reaction was completed, the reaction tube was cooled to room temperature, and after the consumption of the aryl chloride was detected by thin layer chromatography, the reactio...

Embodiment 3

[0027] Example 3: Synthesis of Neopentaneethylene Glycol 1,4-diboronate-2,3,5,6-tetramethylbenzene

[0028] In a 20mL Schlenk tube, add tris(dibenzylideneacetone)dipalladium (0.0092 g, 0.01 mmol) and ligand (palladium:ligand ratio is 1.0mol%:8.0mol%), and then add polytetrafluoroethylene A magnetic stirring bar coated with vinyl fluoride, the system was replaced by nitrogen protection, 0.5 mL of freshly distilled 1,4-dioxane was added, and stirred evenly for 10 minutes while adding to form a palladium complex. Then 1,4-dichloro-2,3,5,6-tetramethylbenzene (0.5 mmol), neopentyl glycol diboronate (1.2 mmol) and cesium acetate (3.0 mmol) were added under a nitrogen atmosphere . Finally 1,4-dioxane solution (1 mL) was added and stirring was continued for 5 minutes at room temperature. Then place the Schlenk tube in a preheated oil bath at 110°C for 24 hours. After the reaction was completed, the reaction tube was cooled to room temperature, and after the consumption of the aryl ...

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Abstract

The invention discloses a preparation method of a high-sterically-hindered arylborate compound. The preparation method includes following steps: in the presence of a catalyst of a catalyst tri(dibenzalacetone)dipalladium with a phosphine ligand (wherein the phosphine ligand is 3-diphenylphosphine-2-(2,6-dimethoxylphenyl)-N-methylindole), adding an aryl chloride, bis(neopentyl glycolato)diboron, and an additive ceseium acetate to a 1,4-dioxane solution; and carrying out a reaction at 100-130 DEG C for 12-48 hours to obtain the arylborate compound. In the invention, the employed substrate is stable, is low in cost and is easy to obtain and the catalyst is unique, is easy to prepare and is suitable for the reaction of the high-sterically-hindered aryl chloride. The system is compatible of existences of functional groups, such as an ester group, an aldehyde group, methoxyl and the like so that range of the substrate is greatly developed. The catalyst system is stable, is high in catalytic activity, is wide in suitable scope, is good in selectivity and is mild in reaction conditions. The high-sterically-hindered arylborate compound can be widely applied in cross coupling reaction catalyzed by transition metal, thereby preparing various compounds, such as biaromatic hydrocarbons. The preparation method has a great application potential in synthesis of natural medicines and drug intermediates.

Description

technical field [0001] The invention belongs to the field of organic chemical synthesis, in particular to a preparation method of high-steric hindered aryl borate compounds. Background technique [0002] Highly hindered aryl borates are a very important class of organic synthesis intermediates with wide application value. Through transition metal-catalyzed cross-coupling reactions, this type of compound can be used to construct a variety of large sterically hindered biaryl compounds, such biaryl compounds are important structural units for the synthesis of many drugs and highly biologically active natural product intermediates . Therefore, it is of great significance to develop synthetic methods for the synthesis of highly hindered aryl borate compounds. However, the preparation of such compounds has so far been quite challenging. The traditional method of synthesizing aryl borate mainly adopts halogen and metal exchange of aryl bromide / iodide (such as aryl magnesium or l...

Claims

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Application Information

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IPC IPC(8): C07F5/02
CPCC07F5/04
Inventor 邝福儿周永健苏秋铭蔡珮盈
Owner THE HONG KONG POLYTECHNIC UNIV SHENZHEN RES INST
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