Method for synthesizing enamine under catalysis of palladium imine complex containing pyridine ligands

A technology for synthesizing enamine and palladium imine, applied in the field of catalytic chemistry, can solve the problems of restricting the development of enamine chemistry, limited types of amino reagents, complicated and difficult preparation, etc., and achieves simple and green synthesis process, variety of catalytic substrates, regional selective effect

Active Publication Date: 2019-08-30
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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  • Method for synthesizing enamine under catalysis of palladium imine complex containing pyridine ligands
  • Method for synthesizing enamine under catalysis of palladium imine complex containing pyridine ligands
  • Method for synthesizing enamine under catalysis of palladium imine complex containing pyridine ligands

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Divalent palladium imine complexes catalyze the hydroamination of phenylacetylene to prepare enamines:

[0035]

[0036] 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 toluene were added to the reaction tube, the reaction temperature was 60°C, and the reaction time was 8h , after the end, the system was extracted with ethyl acetate for 3 times, the concentrated reaction solution was separated by silica gel column chromatography to obtain the corresponding enamine compound, and 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 complexes catalyze the hydroamination of phenylacetylene to prepare enamines:

[0039]

[0040] 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 toluene were added to the reaction tube, the reaction temperature was 75°C, and the reaction time was 6h , after the completion, the system was extracted three times with ethyl acetate, the concentrated reaction solution was separated by silica gel column chromatography to obtain the corresponding enamine compound, and 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 ] The infrared spectrum of Pd=NPh is shown in figure 1 .

Embodiment 3

[0042] Divalent palladium imine complexes catalyze 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), methylisopropylamine (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 three times with ethyl acetate, 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 1.5575 g of the product, with a yield of 89%. 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 ] The infrared spectrum of Pd=NPh is shown in figure 2 .

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Abstract

The invention relates to a method for synthesizing enamine under catalysis of a palladium imine complex containing pyridine ligands. The method comprises steps as follows: phenylacetylene and secondary amine are taken as raw materials, the palladium imine complex containing the pyridine ligands is taken as a catalyst, a hydroamination reaction is performed in a solvent, aftertreatment is performed, and enamine is obtained. Compared with the prior art, the method for preparing enamine compounds through the hydroamination reaction of phenylacetylene under the catalysis of a divalent palladium imine complex containing the pyridine ligands is provided, raw materials are simple and easy to obtain, a synthesis process is simple and green, the method has excellent selectivity and high yield, theatom economy is high, three wastes are reduced, and the method is environmentally friendly, simple and convenient to operate and suitable for industrial synthesis of the high-value enamine compounds.

Description

technical field [0001] The invention belongs to the technical field of catalytic chemistry, and relates to a method for catalytically synthesizing enamine by using a palladium imine complex containing a pyridine ligand. Background technique [0002] Enamine compounds 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 drugs ; In addition, enamines are widely used as intermediates in the preparation of chiral amines. The traditional methods of synthesizing enamine mainly include condensation reaction, addition reaction, heterocyclic cleavage and imine to prepare enamine. There are also some special synthetic methods such as Curtius rearrangement, amide α, β elimination reaction and ketoxime Reductive acylation, etc. These synthetic methods have obvious deficiencies: [0003...

Claims

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Application Information

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Patent Type & Authority Applications(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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