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A kind of nickel-catalyzed direct reductive cross-coupling method and product of heterocyclic phosphonium salt and aryl bromide

A cross-coupling, nickel-catalyzed technology, applied in chemical instruments and methods, organic chemistry, organic substitution, etc., to achieve the effect of green steps, mild reaction conditions and low pollution

Active Publication Date: 2022-04-15
NANJING TECH UNIV
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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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  • A kind of nickel-catalyzed direct reductive cross-coupling method and product of heterocyclic phosphonium salt and aryl bromide
  • A kind of nickel-catalyzed direct reductive cross-coupling method and product of heterocyclic phosphonium salt and aryl bromide
  • A kind of nickel-catalyzed direct reductive cross-coupling method and product of heterocyclic phosphonium salt and aryl bromide

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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Abstract

The invention discloses a direct reductive cross-coupling method and product of a nickel-catalyzed heterocyclic phosphonium salt and an aryl bromide, comprising: heating a mixture of magnesium chips and lithium chloride under a nitrogen atmosphere; Add ultra-dry solvent to it; then add phosphonium salt compound, catalyst, ligand and aryl bromide respectively, stir the reaction; quench, wash, extract and dry the reaction product, and then separate by column chromatography to obtain arylated pyridine or diazine compounds; the preparation method of the invention has 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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Patent Type & Authority Patents(China)
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 TECH UNIV
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