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A kind of method that utilizes the palladium imine complex containing pyridine ligand to catalyze the synthesis of enamine

A technology for synthesizing enamines and palladium imines, which is applied in the field of catalytic chemistry, can solve the problems of limited types of amino reagents, restricting the chemical development of enamines, single type of raw materials, etc., and achieves a variety of catalytic substrates, a simple and green synthesis process, and a catalytic effect. Efficient effect

Active Publication Date: 2022-07-08
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] (2) Low tolerance to different functional groups of the reaction raw materials;
[0005] (3) The types of amino reagents are limited;
[0007] (5) Restrictions on raw materials, such as single types of raw materials, cumbersome and difficult preparations, etc.
[0008] These disadvantages greatly limit the development of enamine chemistry

Method used

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  • A kind of method that utilizes the palladium imine complex containing pyridine ligand to catalyze the synthesis of enamine
  • A kind of method that utilizes the palladium imine complex containing pyridine ligand to catalyze the synthesis of enamine
  • A kind of method that utilizes the palladium imine complex containing pyridine ligand to catalyze the synthesis of enamine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Divalent palladium-imine complex catalyzed the hydroamination of phenylacetylene to prepare enamines:

[0035]

[0036] The catalyst [CH 2 (C 5 H 4 N) 2 ]Pd=NPh (3.7mg, 0.00001mol), phenylacetylene (1.02g, 0.01mol), methylphenylamine (1.02g, 0.01mol) and 6mL of toluene were added to the reaction tube, the reaction temperature was 60°C, and the reaction time was 8h , the system was extracted with ethyl acetate 3 times after the end, and the reaction solution was concentrated and separated by silica gel column chromatography to obtain the corresponding enamine compounds. The obtained product was subjected to LC-MS to obtain 1.9855 g of the product with a yield of 95%. 1 H NMR (500MHz, CDCl 3 ): δ7.88(d, J=7.0Hz, 2H), 7.63-7.51(m, 5H), 7.40-7.33(m, 3H), 6.67(s, 1H), 5.93(s, 1H), 3.05( s,3H). The catalyst used [CH 2 (C 5 H 4 N) 2 ] The infrared spectrum of Pd=NPh is shown in figure 1 .

Embodiment 2

[0038] Divalent palladium-imine complex catalyzed the hydroamination of phenylacetylene to prepare enamines:

[0039]

[0040] The catalyst [CH 2 (C 5 H 4 N) 2 ]Pd=NPh (3.7mg, 0.00001mol), phenylacetylene (1.22g, 0.012mol), methylethylamine (1.02g, 0.01mol) and 10mL of toluene were added to the reaction tube, the reaction temperature was 75°C, and the reaction time was 6h , the system was extracted with ethyl acetate 3 times after the end, and the concentrated reaction solution was separated by silica gel column chromatography to obtain the corresponding enamine compounds. The obtained product was subjected to LC-MS to obtain 1.4973 g of the product with a yield of 93%. 1H NMR (500MHz, CDCl 3 ): δ7.85(d, J=7.0Hz, 2H), 7.48-7.41(m, 3H), 6.67(s, 1H), 5.95(s, 1H), 3.11(brs, 2H), 3.05(s, 3H), 1.83 (t, J=7.0Hz, 3H). The catalyst used [CH 2 (C 5 H 4 N) 2 ]Pd=NPh infrared spectrum see figure 1 .

Embodiment 3

[0042] Divalent palladium-imine complex catalyzed the hydroamination of phenylacetylene to prepare enamines:

[0043]

[0044] The catalyst [(CH 3 )CH(C 5 H 4 N) 2 ]Pd=NPh (3.8mg, 0.00001mol), phenylacetylene (1.53g, 0.015mol), methyl isopropylamine (1.02g, 0.01mol) and 15mL toluene were added to the reaction tube, the reaction temperature was 100°C, and the reaction time was After 12 hours, the system was extracted with ethyl acetate for 3 times, and the reaction solution was concentrated and separated by silica gel column chromatography to obtain the corresponding enamine compounds. 1H NMR (500MHz, CDCl 3 ): δ7.87(d, J=7.0Hz, 2H), 7.47-7.42(m, 3H), 6.65(s, 1H), 5.90(s, 1H), 3.15(brs, 1H), 3.06(s, 3H), 1.85(t, J=7.2Hz, 6H). The catalyst used [(CH3 )CH(C 5 H 4 N) 2 ]Pd=NPh infrared spectrum see figure 2 .

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Abstract

The invention relates to a method for catalyzing and synthesizing enamines by utilizing palladium imine complexes containing pyridine ligands. , the hydroamination reaction occurs in the solvent, and the enamine is obtained after post-treatment. Compared with the prior art, the present invention provides a method for preparing enamine compounds by utilizing a divalent palladium imine complex containing a pyridine ligand to catalyze the hydroamination reaction of phenylacetylene. The raw materials are simple and easy to obtain, and the synthesis process is simple and green. , has excellent selectivity and high yield, high atom economy, reduces the generation of three wastes, is environmentally friendly, easy to operate, and is suitable for industrial synthesis of high-value enamine compounds.

Description

technical field [0001] The invention belongs to the technical field of catalytic chemistry, and relates to a method for catalyzing and synthesizing an enamine by utilizing a palladium imine complex containing a pyridine ligand. Background technique [0002] Enamines play an important role in many fields, such as being used as precursors for the synthesis of various nitrogen-containing heterocyclic derivatives; they also have special medicinal properties and exist as key structural units in many natural products and medicines ; In addition, enamines are widely used in the preparation of chiral amines as intermediates. The traditional methods of synthesizing enamines mainly include condensation reaction, addition reaction, heterocyclic cleavage and imine preparation of enamine, etc. There are also some special synthesis methods such as Curtius rearrangement, amide α, β position elimination reaction and ketoxime. Reductive acylation, etc. These synthetic methods have obvious ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C209/60C07C211/28C07C211/54B01J31/22
CPCC07C209/60B01J31/1815B01J2231/32B01J2531/824C07C211/28C07C211/54Y02P20/584
Inventor 姚子健樊晓楠靳永旭云雪静高永红邓维
Owner SHANGHAI INST OF TECH
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