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Temperature-sensitive chiral amino acid copper complex catalyst and preparation method thereof

A technology of chiral amino acid and amino acid copper, which is applied in the direction of organic compound/hydride/coordination complex catalyst, preparation of organic compound, physical/chemical process catalyst, etc., can solve the problem of difficult catalyst recovery, environmental pollution, water phase catalysis Low efficiency and other problems, to achieve the effects of large-scale industrial production, safe operation, and improvement of catalytic reaction efficiency

Inactive Publication Date: 2019-11-22
HUBEI ENG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The catalyst works well, but the reaction is carried out in an organic solvent, which easily leads to environmental pollution
[0006] In summary, the catalysts currently used in Henry's asymmetric addition reaction have the problems of low catalytic efficiency in aqueous phase and difficult recovery of catalysts.

Method used

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  • Temperature-sensitive chiral amino acid copper complex catalyst and preparation method thereof
  • Temperature-sensitive chiral amino acid copper complex catalyst and preparation method thereof
  • Temperature-sensitive chiral amino acid copper complex catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Cu II -PN 50 A 5 The preparation method comprises steps:

[0050] (1) Synthesis of chiral amino acid compounds containing carbon-carbon double bonds

[0051] Reaction 1

[0052]

[0053] In the above reaction formula 1, R 3 is a hydrogen atom, R 4 is benzyl.

[0054] The specific operation process is to add 10mmol of L-phenylalanine to a 100mL dry three-necked flask, and add 20mL of anhydrous dichloromethane and 11mmol of triethylamine to it, and place the reaction flask in an ice-water bath for magnetic stirring. After the liquid was cooled to 0° C., 30 mL of acryloyl chloride (11 mmol) in dichloromethane solution was slowly added dropwise therein within 30 min. After the dropwise addition, when no steam emerges from the solution, slowly raise the reaction temperature to room temperature, and continue the reaction for 2 to 8 hours. After the reaction was completed, 10 mL of saturated NH 4 Cl solution, CH 2 Cl 2 (2×5ml) to extract the aqueous layer, and th...

Embodiment 2

[0062] The Cu that embodiment 1 obtains II -PN 50 A 5 Used to catalyze the Henry addition reaction; that is, in aqueous medium, aldehydes and nitroalkanes are in Cu II -PN 50 A 5 Under the catalysis of the catalyst, the asymmetric Henry addition reaction is carried out to obtain the β-nitro alcohol compound.

[0063] Aldehyde compounds have the structure of general formula (8); nitroalkanes have the structure of general formula (9); β-nitroalcohol compounds have the structure of general formula (10).

[0064] R 5 -CHO formula (8)

[0065] R 6 -NO 2 Formula (9)

[0066]

[0067] Reaction 3

[0068]

[0069] In this embodiment, the aldehyde compound is benzaldehyde, and the nitroalkane is nitromethane. The specific catalytic process is to add 0.5mmol% catalyst Cu in a 10mL reaction flask. II -PN 50 A 5 , 1mL H 2 O dissolves the catalyst, then adds 1 mmol of substrate (benzaldehyde) and 3 mmol of nitromethane to it, and stirs the reaction at 25°C. Thin-layer ...

Embodiment 3

[0078] The thermosensitive type chiral amino acid copper complex catalyst Cu that embodiment 1 obtains II -PN 50 A 5 Catalysis on different substrates.

[0079] Catalyst Cu II -PN 50 A 5 And the traditional amino acid copper catalyst is used to catalyze the reaction of other aldehydes and nitroalkanes, and the results are shown in Table 2 below:

[0080] Table 2

[0081]

[0082] As can be seen from the table, after 18 hours of reaction, the catalyst Cu II -PN 50 A 5The catalytic effect of the catalyst is significantly better than that of traditional catalysts, and has huge advantages in yield and ee value. This type of catalyst shows good catalytic effect in Henry's asymmetric addition reaction in water phase, and can solve the problem of difficult mass transfer in water phase reaction in industry.

[0083] The characterization data of some products are as follows:

[0084] (R)-1-phenyl-2-nitroalcohol: colorless oil, separated by silica gel column chromatography...

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Abstract

The invention relates to the field of chiral catalyst preparation, in particular to a temperature-sensitive chiral amino acid copper complex catalyst and a preparation method thereof. The invention relates to a preparation method of a temperature-sensitive chiral amino acid copper complex catalyst, which comprises the following steps: (1) reacting chiral amino acid with acyl chloride containing double bonds, thereby introducing unsaturated carbon-carbon double bonds into the chiral amino acid to obtain a chiral amino acid compound containing carbon-carbon double bonds; (2) carrying out polymerization reaction on the chiral amino acid compound containing the carbon-carbon double bonds and N-isopropylacrylamide to obtain a temperature-sensitive chiral amino acid block polymer; and (3) finally, carrying out self-folding on the temperature-sensitive chiral amino acid block polymer under the action of metal copper salt through coordination to form the temperature-sensitive chiral amino acidcopper complex. The catalyst obtained by the invention not only improves the catalytic reaction efficiency of asymmetric Henry addition reaction in a pure water phase, but also has the characteristics of simple recovery and excellent reusability.

Description

technical field [0001] The invention relates to the field of chiral catalyst preparation, in particular to a temperature-sensitive chiral amino acid copper complex catalyst and a preparation method thereof. Background technique [0002] Chiral β-nitroalcohol compounds are a class of bifunctional compounds with a wide range of uses. At present, the most effective way to obtain β-nitroalcohols with a single chirality is to obtain them through asymmetric catalytic reactions, that is, asymmetric Henry addition reactions directly occur between nitroalkanes and aldehydes under the action of chiral catalysts to obtain chiral β-nitroalcohols. The asymmetric catalysts used in the Henry reaction mainly include oxazoline catalysts, chiral diamine catalysts, Schiff base catalysts, and alkaloid complex catalysts. [0003] In 2002, the Danish chemist (C. Christensen, K. Juhl, R.G. Hazell and K. The Journal of Organic Chemistry 2002, 67, 4875-4881.) first reported the use of bisoxazol...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C201/12C07C205/16C07C205/26C07C253/30
CPCB01J31/223B01J31/1805C07C201/12C07C253/30B01J2531/16B01J2231/34C07C205/16C07C205/26C07C255/53
Inventor 张瑶瑶王锋丁瑜付争兵杜军
Owner HUBEI ENG UNIV
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