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Method for preparing functionalized polysubstituted aromatic hydrocarbon through cascade reaction

A series reaction and multi-substitution technology is applied in the relay reaction between organic antimony compounds and polyhalogenated aromatic hydrocarbons to prepare functionalized multi-substituted aromatic hydrocarbons, and in the field of synthesizing functionalized multi-substituted aromatic hydrocarbons, which can solve the problems of unknown series reaction of organic antimony compounds.

Pending Publication Date: 2021-10-08
HUNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the study of tandem reactions using this strategy to synthesize complex molecules has attracted attention (J.Am.Chem.Soc.2018, 140, 2693; Chem.Lett.2021, 50, 180), the tandem reactions involving organoantimony compounds still unknown

Method used

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  • Method for preparing functionalized polysubstituted aromatic hydrocarbon through cascade reaction
  • Method for preparing functionalized polysubstituted aromatic hydrocarbon through cascade reaction
  • Method for preparing functionalized polysubstituted aromatic hydrocarbon through cascade reaction

Examples

Experimental program
Comparison scheme
Effect test

preparation example 1

[0028] (1) Add organic antimony compound 55 (0.3 mmol), 1-bromo-3-iodo-5-toluene 29a (R 3 =5-Me) (0.3mmol), 1,2-bis(diphenylphosphine)ethane nickel chloride (0.015mmol), 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (0.015 mmol), lithium iodide (0.6mmol), zinc powder (0.3mmol) and tetrahydrofuran (2.0mL), react at 100°C for 12h. After the reaction was completed, the solvent was removed under reduced pressure, and the pure compound was separated by column chromatography with a yield of 92%.

[0029] (2) the product (0.3mmol) obtained in the first step, 4-bromobenzonitrile 54a (R 2 =4-CN) (0.3mmol), palladium acetate (0.015mmol), n-butylphosphine bromide (0.06mmol), cesium carbonate (0.6mmol) and tetrahydrofuran (2.0mL) were added in the 25 ml reactor according to the proportion , stirred at 110°C for 12 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the pure compound was obtained by column chromatography with a yield of 91%.

[0030...

preparation example 2

[0032] (1) Add organic antimony compound 55 (0.3 mmol), 1-bromo-3-iodo-5-ethylbenzene 29b (R 3 =5-Et) (0.3mmol), 1,2-bis(diphenylphosphine)ethane nickel chloride (0.015mmol), 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (0.015 mmol), lithium iodide (0.6mmol), zinc powder (0.3mmol) and tetrahydrofuran (2.0mL), react at 100°C for 12h. After the reaction was completed, the solvent was removed under reduced pressure, and the pure compound was separated by column chromatography with a yield of 94%.

[0033] (2) the product (0.3mmol) obtained in the first step, 4-bromobenzonitrile 54a (R 2=4-CN) (0.3mmol), palladium acetate (0.015mmol), n-butylphosphine bromide (0.06mmol), cesium carbonate (0.6mmol) and tetrahydrofuran (2.0mL) were added in the 25 ml reactor according to the proportion , stirred at 110°C for 12 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the pure compound was obtained by column chromatography with a yield of 92%.

[...

preparation example 3

[0036] (1) Add organic antimony compound 55 (0.3 mmol), 1-bromo-3-iodo-5-butylbenzene 29c (R 3 =5-Bu) (0.3mmol), 1,2-bis(diphenylphosphine)ethane nickel chloride (0.015mmol), 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (0.015 mmol), lithium iodide (0.6mmol), zinc powder (0.3mmol) and tetrahydrofuran (2.0mL), react at 100°C for 12h. After the reaction was completed, the solvent was removed under reduced pressure, and the pure compound was obtained by column chromatography with a yield of 90%.

[0037] (2) the product (0.3mmol) obtained in the first step, 4-bromobenzonitrile 54a (R 2 =4-CN) (0.3mmol), palladium acetate (0.015mmol), n-butylphosphine bromide (0.06mmol), cesium carbonate (0.6mmol) and tetrahydrofuran (2.0mL) were added in the 25 ml reactor according to the proportion , stirred at 110°C for 12 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the pure compound was obtained by column chromatography with a yield of 89%.

[...

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Abstract

The invention aims to provide a method for preparing functionalized polysubstituted aromatic hydrocarbon through cascade reaction. A tandem catalytic system comprises multi-step nickel catalysis and palladium catalysis processes; and according to the synthesis method, palladium acetate, palladium chloride, 1,2-bis(diphenylphosphine)ethane nickel chloride and nickel chloride are used as catalysts, an organic antimony compound and polyhalogenated aromatic hydrocarbon are used as coupling reagents, and functionalized aromatic hydrocarbon and a drug derivative are obtained through a series of tandem reactions. The method has the advantages of high yield, high selectivity, simplicity and convenience in operation and the like.

Description

【Technical field】 [0001] The invention relates to the field of organic synthesis, and relates to a method for synthesizing functionalized polysubstituted aromatic hydrocarbons, in particular to the preparation of functionalized polysubstituted aromatic hydrocarbons through the relay reaction between organic antimony compounds and polyhalogenated aromatic hydrocarbons by using metallic nickel and palladium as catalysts. 【Background technique】 [0002] Polyaromatic hydrocarbons widely exist in natural products, medicine and functional organic materials (Adv. Mater. 2007, 19, 197; J. Am. Chem. Soc. 2004, 126, 3378). Transition metal-catalyzed coupling reactions between aryl halides and organometallic reagents are powerful tools for the synthesis of polyarylarenes. Although the study of tandem reactions using this strategy to synthesize complex molecules has attracted attention (J.Am.Chem.Soc.2018, 140, 2693; Chem.Lett.2021, 50, 180), the tandem reactions involving organoantimon...

Claims

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Application Information

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IPC IPC(8): C07C2/86C07C15/14C07C41/30C07C43/205C07C17/269C07C25/18
CPCC07C2/861C07C41/30C07C17/269C07C15/14C07C43/205C07C25/18
Inventor 邱仁华张德奖徐芝尹双凤神户宣明
Owner HUNAN UNIV
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