Nickel-catalyzed heterocyclic phosphonium salt and aryl bromide direct reduction cross-coupling method and product

A cross-coupling, nickel-catalyzed technology, applied in chemical instruments and methods, organic chemistry, organic substitution, etc., to achieve mild reaction conditions, expand the scope of preparation of substrates, and reduce pollution.

Active Publication Date: 2021-09-14
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in their report, relatively more expensive palladium catalysts and silver salts were used
Furthermore, this reaction is only applicable to the more expensive aryl iodides

Method used

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  • Nickel-catalyzed heterocyclic phosphonium salt and aryl bromide direct reduction cross-coupling method and product
  • Nickel-catalyzed heterocyclic phosphonium salt and aryl bromide direct reduction cross-coupling method and product
  • Nickel-catalyzed heterocyclic phosphonium salt and aryl bromide direct reduction cross-coupling method and product

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] (1) Put the sealed tube equipped with a magnetic stirrer in an oven to dry for one hour, take it out and plug it with a rubber stopper while it is hot and insert a nitrogen balloon; then weigh magnesium chips (65.4mg, 1.5mmol, 3equiv. ) and lithium chloride (84.7mg, 2mmol, 4equiv.) and added to the sealed tube; then under reduced pressure, use an electric heating gun to heat the mixture of magnesium chips and lithium chloride (320 ° C, 3 minutes);

[0036] (2) After the mixture was cooled to room temperature, 2 mL of ultra-dry tetrahydrofuran was added thereto, and then the tube was sealed and replaced with nitrogen three times. Subsequently, triphenyl(pyridin-4-yl)phosphonium trifluoromethanesulfonate (244.7 mg, 1 mmol, 1 equiv.), bistriphenylphosphine palladium nickel dichloride (65.4 mg, 0.1 mmol , 20mol%), 1,10-phenanthroline-5,6-dione (21.0mg, 0.1mmol, 20mol%), bromobenzene (236.4mg, 1.5mmol, 3equiv.); the mixture was stirred at room temperature for 12 hours ;

...

Embodiment 2

[0042] (1) Put the sealed tube equipped with a magnetic stirrer in an oven to dry for one hour, take it out and plug it with a rubber stopper while it is hot and insert a nitrogen balloon; then weigh magnesium chips (65.4mg, 1.5mmol, 3equiv. ) and lithium chloride (84.7mg, 2mmol, 4equiv.) and added to the sealed tube; then under reduced pressure, use an electric heating gun to heat the mixture of magnesium chips and lithium chloride (320 ° C, 3 minutes);

[0043] (2) When the mixture was cooled to room temperature, 2 mL of ultra-dry tetrahydrofuran was added to it, and then the sealed tube was replaced with nitrogen three times; then triphenyl(pyridin-4-yl)phosphonium trifluoromethanesulfonate was added to the sealed tube respectively (244.7mg, 1mmol, 1equiv.), bistriphenylphosphine palladium nickel dichloride (65.4mg, 0.1mmol, 20mol%), 1,10-phenanthroline-5,6-dione (21.0mg, 0.1 mmol, 20mol%), 3-bromo-N,N-dimethylaniline (300.4mg, 1.5mmol, 3equiv.); the mixture was stirred at ...

Embodiment 3

[0049] (1) Put the sealed tube equipped with a magnetic stirrer in an oven to dry for one hour, take it out and plug it with a rubber stopper while it is hot and insert a nitrogen balloon; then weigh magnesium chips (65.4mg, 1.5mmol, 3equiv. ) and lithium chloride (84.7mg, 2mmol, 4equiv.) and added to the sealed tube; then under reduced pressure, use an electric heating gun to heat the mixture of magnesium chips and lithium chloride (320 ° C, 3 minutes);

[0050] (2) When the mixture was lowered to room temperature, 2 mL of ultra-dry tetrahydrofuran was added thereto, and then the sealed tube was replaced with nitrogen three times; then (4-triphenylphosphonium quinoline) trifluoromethanesulfonate (4-triphenylphosphonium quinoline) triflate ( 269.6mg, 1mmol, 1equiv.), bistriphenylphosphine palladium nickel dichloride (65.4mg, 0.1mmol, 20mol%), 1,10-phenanthroline-5,6-dione (21.0mg, 0.1mmol , 20mol%), bromobenzene (236.4mg, 1.5mmol, 3equiv.); the mixture was stirred at room temp...

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PUM

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Abstract

The invention discloses a nickel-catalyzed heterocyclic phosphonium salt and aryl bromide direct reduction cross-coupling method and a product, and the method comprises the following steps: in a nitrogen atmosphere, heating a mixture of magnesium chips and lithium chloride; cooling the mixture to room temperature, and adding an ultra-dry solvent into the mixture; then respectively adding a phosphonium salt compound, a catalyst, a ligand and aryl bromide, and stirring to react; and quenching, washing, extracting and drying the reaction product, and separating by column chromatography to obtain the arylated pyridine or diazine compound. The preparation method has the characteristics of mild reaction conditions, simple post-treatment, green steps, low pollution, high economic benefits and the like.

Description

technical field [0001] The invention belongs to the technical field of organic compound synthesis, and specifically relates to a nickel-catalyzed direct reductive cross-coupling method and product of heterocyclic phosphonium salt and aryl bromide. Background technique [0002] Organic molecules containing pyridine or diazine moieties are widely found in pharmaceuticals, agrochemicals, materials, ligands, and natural products. Therefore, the development of efficient methods for the construction of pyridine and diazine heterocycles has received extensive attention. In this regard, recent efforts by the McNally Research Laboratory have pioneered the demonstration that pyridyl or diazinylphosphonium salts are readily accessible via the reaction of pyridines or diazines with triarylphosphines as multifunctional electrophiles. A wide range of organic transformations, such as halogenation, alkoxylation, deuteration, fluoroalkylation, and amination, lead to heterocyclic compounds o...

Claims

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Application Information

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IPC IPC(8): C07D213/16C07D213/127C07D213/38C07D215/06C07D213/26C07D213/30C07D409/04C07D241/42C07D241/12C07B37/04
CPCC07D213/16C07D213/127C07D213/38C07D215/06C07D213/26C07D213/30C07D409/04C07D241/42C07D241/12C07B37/04
Inventor 沈志良褚雪强崔艳影
Owner NANJING UNIV OF TECH
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