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Method for catalyzing asymmetric Michael addition reaction and catalyst

An addition reaction and asymmetric technology, applied in catalytic reactions, physical/chemical process catalysts, organic chemical methods, etc., can solve the problems of low catalytic efficiency, difficult catalyst preparation, poor stability, etc., and achieve high catalytic efficiency and rich variety , the effect of mild process conditions

Active Publication Date: 2019-10-25
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] The technical problem to be solved in the present invention is: in order to overcome the problems such as difficult preparation of asymmetric Michael addition reaction catalyst in the prior art, catalytic efficiency is low, poor stability, etc., provide a kind of calix [4] square amide cyclohexanediamine derivative catalyst Method of Asymmetric Michael Addition Reaction

Method used

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  • Method for catalyzing asymmetric Michael addition reaction and catalyst
  • Method for catalyzing asymmetric Michael addition reaction and catalyst
  • Method for catalyzing asymmetric Michael addition reaction and catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] The present embodiment is the preparation method of calix [4] squaramide cyclohexanediamine catalyst I and II, and the specific synthesis method is as follows:

[0027] Synthesis of Calix[4]Squaramide Cyclohexanediamine Catalysts I and II

[0028]

[0029] Respectively, 1a (0.332g, 0.5mmol) or 1b (0.339g, 0.5mmol), dimethyl squarylate (0.074g, 0.52mmol / 0.149g, 1.05mmol) were heated to reflux in 8mL MeOH solution, followed by TLC spot plate Reaction process, stop the reaction after the disappearance of raw materials, evaporate the solvent, and separate and purify the crude product by column chromatography (ethyl acetate:petroleum ether=1:10) to obtain white solid 2a (0.341g, yield 88%) and light yellow Solid 2b (0.369 g, 82% yield).

[0030] 2a. Mp: 202-204°C; 1 H NMR (300MHz, DMSO-d 6 ):δ=0.98(dt,J 1 =7.2Hz,J 2 =2.1Hz,12H),1.41-1.48(m,8H),1.82-1.90(m,8H),3.15(t,J=12.9Hz,4H),3.81(t,J=6.9Hz,8H),4.31 -4.35(m,4H),4.35(s,3H),6.48-6.66(m,11H),10.44(s,1H). 13 C NMR (...

Embodiment 2

[0036] In this example, using β-nitrostyrene and acetylacetone as substrates, the activity of the asymmetric Michael addition reaction catalyzed by the calix[4]squaramide cyclohexanediamine derivatives I and II was confirmed. The experimental method is: Weigh β-nitrostyrene (0.5mmol, 0.075g), acetylacetone (1mmol, 0.100g) and catalyst (5mol% of β-nitrostyrene) into 1mL dichloromethane In a test tube, stir at 25°C and react for 4 hours. The reaction was stopped, the solvent was concentrated, and separated by column chromatography (ethyl acetate:petroleum ether) to obtain the Michael addition product, and the optical selectivity (ee) of the product was analyzed by HPLC.

[0037] Table 1 The reaction results of β-nitrostyrene and acetylacetone under the catalysis of different catalysts

[0038]

[0039] The results are shown in Table 1. It can be seen that when the calix[4] squaramide cyclohexanediamine derivatives I and II are used as catalysts, the catalyst II with two cata...

Embodiment 3

[0048] In this embodiment, β-nitrostyrene and acetylacetone are used as substrates, and the main influencing factors of the asymmetric Michael addition reaction catalyzed by calix [4] squaramide cyclohexanediamine derivative II are solvent type, reaction temperature, The reaction time and catalyst dosage were systematically studied.

[0049] Result is shown in table 2, 3 and 4, therefore the optimal experimental condition of the asymmetric Michael addition reaction of calix [4] squaramide cyclohexanediamine derivative II catalysis is: catalyst consumption is 5mol%, methylene chloride is used as solvent, the reaction temperature is 25°C.

[0050] Table 2 The influence of temperature on the asymmetric Michael addition reaction catalyzed by calix [4] squaramide cyclohexanediamine derivative II

[0051]

[0052] Table 3 The influence of solvents on the asymmetric Michael addition reaction catalyzed by calix[4]squaramide cyclohexanediamine derivative II

[0053]

[0054] Ta...

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Abstract

The invention belongs to the technical field of catalytic organic synthesis and particularly relates to a method for catalyzing an asymmetric Michael addition reaction and a catalyst. Nitroolefin and1,3-dicarbonyl ketone are taken as raw materials, a calix[4]squaramide-diaminocyclohexane derivative is taken as a catalyst, dichloromethane is taken as a solvent, the Michael addition catalytic reaction is conducted, after the reaction is completed, the solvent is concentrated, and a product is obtained through silica gel column chromatographic separation. The calix[4]squaramide-diaminocyclohexane catalyst is mild in synthetic process condition and high in catalytic efficiency, the good ee value can be obtained through the catalytic reaction under the room temperature condition, and wide application prospects are realized.

Description

technical field [0001] The invention belongs to the technical field of catalytic organic synthesis, and in particular relates to a method for catalytic asymmetric Michael addition reaction and a catalyst thereof. Background technique [0002] In the past two decades, chiral catalysts containing hydrogen bond donors have been gradually developed and used by chemists. Among these chiral catalysts with different hydrogen donors, chiral catalysts with thiourea as the core structure dominate the field, and catalysts with other hydrogen donor structures have rarely been developed. The square amide catalyst is a chiral catalyst with both nucleophilic and electrophilic properties based on the research of chiral thiourea. It also has electron-donating and electron-accepting hydrogen bond properties, and has a unique rigid structure, so its potential value is gradually being tapped by chemists. [0003] In the prior art, square amide catalysts are usually used in asymmetric Michael ...

Claims

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Application Information

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IPC IPC(8): C07C201/12C07C205/45C07C225/20C07C221/00B01J31/02
CPCC07C201/12C07C225/20C07C221/00B01J31/0271C07C2601/04C07C2601/12C07C2603/92C07B2200/07B01J2231/346C07C205/45
Inventor 李正义童洪笑殷乐杨科孙小强
Owner CHANGZHOU UNIV
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