Calix[4]squaramide cyclohexanediamine derivative and method for catalyzing asymmetric Michael addition and acetalization tandem reaction by using derivative

A cyclohexanediamine, series reaction technology, applied in the field of catalytic organic synthesis, can solve the problems of low catalytic efficiency, difficult catalyst preparation, etc., and achieve the effects of high catalytic efficiency, mild synthesis process conditions, and broad industrial application prospects.

Active Publication Date: 2019-09-27
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved in the present invention is: in order to overcome the problems such as the difficult preparation of the catalyst for the series reaction of asymmetric Michael addition and acetalization in the prior art, and the low catalytic efficiency, a kind of calix[4] squaramide cyclohexanediamine derivative is provided. Compounds and their method for catalyzing asymmetric Michael addition and acetalization tandem reactions

Method used

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  • Calix[4]squaramide cyclohexanediamine derivative and method for catalyzing asymmetric Michael addition and acetalization tandem reaction by using derivative
  • Calix[4]squaramide cyclohexanediamine derivative and method for catalyzing asymmetric Michael addition and acetalization tandem reaction by using derivative
  • Calix[4]squaramide cyclohexanediamine derivative and method for catalyzing asymmetric Michael addition and acetalization tandem reaction by using derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] The present embodiment is the preparation method of calix [4] squaramide cyclohexanediamine catalyst I, and the specific synthetic method is as follows:

[0024] Synthesis of Calix[4]Squaramide Cyclohexanediamine Catalyst I

[0025]

[0026] 1a (0.339g, 0.5mmol) and dimethyl squarylate (0.149g, 1.05mmol) were heated to reflux in 8mL of MeOH solution, and the reaction process was tracked by TLC. After the raw materials disappeared, the reaction was stopped, and the solvent was evaporated to obtain the crude product Separation and purification by column chromatography (ethyl acetate: petroleum ether = 1:10) gave light yellow solid 2a (0.369 g, yield 82%).

[0027] 2a.mp:>300℃; 1 H NMR (300MHz, DMSO-d 6 ): δ=0.97(t, J=6.9Hz, 12H), 1.39-1.46(m, 8H), 1.82-1.90(m, 8H), 3.13(d, J=13.5Hz, 4H), 3.78-3.87( m, 8H), 4.33(d, J=12.6Hz, 4H), 6.57-6.76(m, 10H), 10.33(s, 2H). 13 C NMR (75MHz, DMSO-d 6 ):14.4,19.3,19.4,30.8,32.2,32.3,60.8,75.0,120.0,122.4,128.4,132.2,134.4,135.8,...

Embodiment 2

[0031] In this embodiment, 2-oxo-4-phenylbut-3-enoic acid ethyl ester and 1,3-cyclohexanedione are used as substrates to catalyze the calix [4] square amide cyclohexanediamine derivative I The main influencing factors of the cascade reaction of asymmetric Michael addition and acetalization, such as solvent type, reaction temperature, reaction time, and catalyst dosage, were systematically studied.

[0032]

[0033] HPLC analysis method of product:

[0034]High performance liquid chromatography: Shimadzu LC-20A; Chromatographic column: Chiralcel OD-H (Daicel, 250mm×4.6mm, 5μm) silica gel coated with cellulose-tris(3,5-xylylcarbamate) ) chiral chromatography column; mobile phase: n-hexane / isopropanol; detection wavelength: 254nm; flow rate: 0.7mL / min; injection volume: 10μL; column temperature: 25°C.

[0035] Table 1 shows the effect of solvent on the series reaction of asymmetric Michael addition and acetalization catalyzed by calix[4]squaramide cyclohexanediamine derivativ...

Embodiment 3

[0049] In this example, referring to the best experimental conditions in Example 3, the scope of application of unsaturated ketoesters in the series reaction of asymmetric Michael addition and acetalization catalyzed by calix[4]squaramide cyclohexanediamine I was investigated.

[0050] The experimental method is: add unsaturated ketoester (0.5mmol), 1,3-cyclohexanedione (0.55mmol) and calix[4] squaramide cyclohexanediamine derivative I (0.0125mmol) to the container In a test tube of 4mL dichloromethane, magnetically stirred, the reaction solution was reacted at 25°C, the reaction time was 2 to 8 hours, and the TLC plate was used to track the reaction process until the raw materials disappeared. After the reaction, the organic phase was concentrated and passed through silica gel column chromatography. The obtained compound was isolated and purified (ethyl acetate and petroleum ether), and the optical selectivity (ee) of the product was analyzed by HPLC. The experimental results...

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Abstract

The invention belongs to the technical field of catalytic organic synthesis, and specifically relates to a calix[4]squaramide cyclohexanediamine derivative and a method for catalyzing an asymmetric Michael addition and acetalization tandem reaction by using the derivative. With an unsaturated keto ester and 1,3-dicarbonyl cycloketone as raw materials, the calix[4]squaramide cyclohexanediamine derivative as a catalyst, and dichloromethane as solvent, the Michael addition and acetalization tandem catalytic reaction is performed; after the reaction is finished, the solvent is concentrated and a product is obtained through separation by silica gel column chromatography. A calix[4]squaramide cyclohexanediamine catalyst involved in the invention is mild in synthesis process conditions, the separation of an intermediate is not needed, the catalytic efficiency is high, a relatively good ee value can be obtained by the catalytic reaction under the condition of room temperature, and broad 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 calix[4] squaramide cyclohexanediamine derivative and its catalytic asymmetric Michael addition and acetalization series reaction method. Background technique [0002] The Michael addition reaction of 1,3-dicarbonyl compounds with β,γ-unsaturated carbonyl compounds is a very important reaction in organic synthesis, and its products have biological and pharmaceutical activities. Unsaturated ketoesters are a class of multifunctional compounds containing carbon-carbon unsaturated bonds (alkenyl or alkynyl), ketone carbonyl and ester groups, and have high reactivity and unique reaction diversity in structure. With the continuous exploration and research of chemists, unsaturated ketoesters have been introduced into the series reaction, many new synthesis methods have been developed, and a large number of new heterocyclic compounds have been created. ...

Claims

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Application Information

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IPC IPC(8): C07C225/20C07C221/00B01J31/02C07B53/00C07D311/74C07D311/92C07D493/04
CPCC07C225/20B01J31/0237B01J31/0271C07D311/74C07D311/92C07D493/04C07B53/00C07C2601/14C07C2601/04C07C2603/92C07B2200/07
Inventor 李正义童洪笑殷乐杨科孙小强
Owner CHANGZHOU UNIV
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