Application of cyclopalladated ferrocenylimine-phosphine adduct in synthesis of asymmetric biaryl compound

A ferrocene imine ring palladium, adduct technology, applied in the preparation of organic compounds, the preparation of amino compounds from amines, organic compounds/hydrides/coordination complex catalysts, etc. To obtain the ideal yield, difficult separation of the target product, etc., to achieve the effects of mild reaction conditions, wide applicability, and strong reaction specificity

Inactive Publication Date: 2011-07-20
ZHENGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] When using the BSC reaction to prepare asymmetric biaryl compounds, in order to make the generated boronate enough to maintain the next C-C coupling, some literature reports the first Halogenated aromatic hydrocarbons need a large excess, which causes too much self-coupling in the Suzuki-Miyaura reaction, which causes certain difficulties in the separation of the target product
In addition, most catalytic systems need to add Pd catalyst in the Suzuki-Miyaura coupling reaction, otherwise the reaction cannot proceed or it is difficult to obtain the desired yield

Method used

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  • Application of cyclopalladated ferrocenylimine-phosphine adduct in synthesis of asymmetric biaryl compound
  • Application of cyclopalladated ferrocenylimine-phosphine adduct in synthesis of asymmetric biaryl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Preparation of 4-acetylbiphenyl

[0030] Take 0.012 mmol of ferroceneimine cyclopalladium-tricyclohexylphosphine adduct, 0.72 mmol of pinacol diboronate, and 1.2 mmol of KOAc into a 10 ml Schlenk tube, and repeatedly vacuumize and fill with N 2 5 times. N 2 Add 0.6 mmol bromobenzene and 2 ml 1,4-dioxane under protection. Stir at room temperature for 5 min, then place in an oil bath heated to 100 °C, and react for 2 h. Suspend the reaction and cool to room temperature. N 2 Add 4-bromoacetophenone 0.5 mmol, 1 ml 1,4-dioxane, 0.5 ml K 3 PO 4 aqueous solution (5M), heated to 100°C, and continued to react for 3 h. Stop the reaction and cool to room temperature. The reaction solution was diluted with ethyl acetate, filtered, washed once with water, and the organic phase was washed with Na 2 SO 4 Dry, filter and concentrate. The residue was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 20 as a developing solvent to obtain 91 mg of the ...

Embodiment 2

[0032] Preparation of 4-acetylbiphenyl

[0033] Take 0.012 mmol of ferroceneimine cyclopalladium-tricyclohexylphosphine adduct, 0.72 mmol of pinacol diboronate, and 1.2 mmol of KOAc into a 10 ml Schlenk tube, and repeatedly vacuumize and fill with N 2 5 times. N 2 Add 0.6 mmol bromobenzene and 2 ml 1,4-dioxane under protection. Stir at room temperature for 5 min, then place in an oil bath heated to 100 °C, and react for 2 h. Suspend the reaction and cool to room temperature. N 2 Add 4-bromoacetophenone 0.5 mmol, 1 ml 1,4-dioxane, 0.5 ml Na t Aqueous OBu solution (5M) was heated to 100°C, and the reaction was continued for 3 h. Stop the reaction and cool to room temperature. The reaction solution was diluted with ethyl acetate, filtered, washed once with water, and the organic phase was washed with Na 2 SO 4 Dry, filter and concentrate. The residue was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 20 as a developing solvent to obtain 91 ...

Embodiment 3

[0035]Take 0.012 mmol of ferroceneimine cyclopalladium-tricyclohexylphosphine adduct, 0.72 mmol of pinacol diboronate, and 1.2 mmol of KOAc into a 10 ml Schlenk tube, and repeatedly vacuumize and fill with N 2 5 times. N 2 Add 0.6 mmol bromobenzene and 2 ml 1,4-dioxane under protection. Stir at room temperature for 5 min, then place in an oil bath heated to 100 °C, and react for 2 h. Suspend the reaction and cool to room temperature. N 2 Add 4-bromoacetophenone 0.5 mmol, 1 ml DMF, 0.5 ml K to the system under atmosphere 3 PO 4 aqueous solution (5M), heated to 100°C, and continued to react for 3 h. Stop the reaction and cool to room temperature. The reaction solution was diluted with ethyl acetate, filtered, washed once with water, and the organic phase was washed with Na 2 SO 4 Dry, filter and concentrate. The residue was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 20 as a developing solvent to obtain 91 mg of the target product with ...

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Abstract

The invention belongs to the technical field of organic synthesis, and in particular relates to an application of a cyclopalladated ferrocenylimine-phosphine adduct in synthesis of an asymmetric biaryl compound. In synthesis of the asymmetric biaryl compound, the cyclopalladated ferrocenylimine-phosphine adduct is utilized as a catalyst, and the catalyst has the advantages of good stability, efficient catalytic activity and wide applicability; and by utilizing the catalyst, a corresponding coupling product with high yield (up to 95%) can be obtained on the premise of smaller catalytic amount, and the synthesis process has the characteristics of mild reaction conditions, wide substrate range and strong reaction specificity.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and particularly relates to the application of ferrocenimine cyclopalladium-phosphine adducts in the synthesis of asymmetric biaryl compounds. Background technique [0002] Unsymmetrical biaryl compounds have important application value in pharmaceutical production, organic synthesis and asymmetric catalysis. Palladium-catalyzed Suzuki-Miyaura coupling to prepare asymmetric biaryls is the most common method. In recent years, chemists have been trying palladium-catalyzed BSC (borylation / Suzuki-Miyaura cross-coupling) reaction to prepare asymmetric biaryl compounds in a "one-pot" way. Several catalytic systems have been successfully applied to this reaction, achieving good results for different substrates. This method avoids the disadvantage that the aryl borate is not easy to separate, and the yield is good, so it has broad application prospects in biomedicine. [0003] When using the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07B37/00C07C49/784C07C45/68C07C43/205C07C41/30C07C205/06C07C201/12C07C211/46C07C209/68C07C43/225C07C255/50C07C253/30C07D213/127C07D213/73C07D213/61C07D213/22C07D213/84C07D213/74C07D213/64
Inventor 崔秀灵吴养洁王连会李敬亚吴豫生朱志兀
Owner ZHENGZHOU UNIV
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