Calix [4] proline derivative and green catalytic asymmetric Aldol reaction method thereof

A proline and derivative technology, applied in the field of catalytic organic synthesis, can solve the problems of difficult catalyst preparation, low catalytic efficiency, poor stability, etc., and achieve the effects of easy industrial production, high catalytic efficiency, and mild synthesis process conditions

Active Publication Date: 2013-12-25
枣庄市新星钢结构有限公司
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Problems solved by technology

[0005] The technical problem to be solved in the present invention is: in order to overcome the problems such as the difficult preparation of asymmetric Aldol reaction catalyst, low catal

Method used

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  • Calix [4] proline derivative and green catalytic asymmetric Aldol reaction method thereof
  • Calix [4] proline derivative and green catalytic asymmetric Aldol reaction method thereof
  • Calix [4] proline derivative and green catalytic asymmetric Aldol reaction method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0026] This embodiment is the preparation method of calix[4]proline catalysts I~III, and the specific synthesis method is as follows:

[0027] One, the synthesis of calix [4] proline catalyst I

[0028]

[0029] 5-Hydroxy-25,26,27,28-tetrapropoxycalix[4]arene (0.61g, 1mmol), (2S,4R)-Cbz-Bn-4-hydroxyproline were put into 100mL three-necked flask respectively (0.39g, 1.1mmol), triphenylphosphine (0.39g, 1.5mmol) and dry toluene (50mL), slowly added dicarbimide isopropyl ester (DIAD) (0.30g, 1.5 mmol), after the dropwise addition, the mixture was refluxed and stirred for 3 days under nitrogen protection. Cool to room temperature, concentrate under reduced pressure, and then separate and purify by column chromatography (petroleum ether / ethyl acetate=3:1) to obtain 0.80 g of intermediate with a yield of 85%.

[0030] Mp: 40~41℃; 1 H NMR (300MHz, CDCl 3 ):δ=7.36-7.20(m,10H,ArH),6.57-6.41(m,9H,ArH),5.87-5.82(m,2H,ArH),5.22-4.96(m,4H,COOCH 2 ),4.46-4.45(m,2H,OCH+NCH),4.43-4.37...

Embodiment 2

[0046] In this example, using p-nitrobenzaldehyde and cyclohexanone as substrates, the activity and structure-activity relationship of the direct asymmetric Aldol reaction catalyzed by the calix[4]proline derivatives I-III were confirmed. The experimental method is as follows: Weigh p-nitrobenzaldehyde (1mmol), cyclohexanone (3mmol) and calixarene proline catalyst (0.02mmol) into test tubes filled with water (18mmol), and stir at 25°C , reacted for 24 hours. Stop the reaction, add dichloromethane (2 mL), extract and separate the organic phase, extract the aqueous phase with dichloromethane (2 mL), combine the organic phases, wash with saturated brine (2 mL), and dry over anhydrous sodium sulfate. After separation by column chromatography (ethyl acetate:petroleum ether=1:5), the Aldol addition product was obtained.

[0047] The results are shown in Table 1. It can be seen that when calix[4]proline (III) is used as a catalyst, the reaction results are the best.

[0048]

[...

Embodiment 3

[0056] In this example, p-nitrobenzaldehyde and cyclohexanone are used as substrates, referring to the experimental method of Example 2, the main influencing factors of the direct asymmetric Aldol reaction catalyzed by calix [4] proline (III) such as the amount of water , substrate ratio, catalyst dosage and reaction temperature were systematically studied.

[0057]The results are shown in Table 2. The experimental result numbered 4 is the best, so the best experimental conditions for the direct asymmetric Aldol reaction catalyzed by calix[4]proline (III) are: p-nitrobenzaldehyde / cyclohexanone / water=1:3:28 (molar ratio), the catalyst dosage is 2mol% (relative to aldehyde), and the reaction temperature is 25°C.

[0058] Table 2 Effects of different experimental conditions on the asymmetric Aldol reaction catalyzed by calix[4]proline(III)

[0059]

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Abstract

The invention relates to a calix [4] proline derivative and a green catalytic asymmetric Aldol reaction method thereof. The method comprises the steps of using aromatic aldehyde and naphthenone as raw materials, the calix [4] proline derivative as a phase transfer catalyst, and water as a solvent for Aldol catalytic reaction at 10-35 DEG C for 12-96h, adding dichloromethane after the reaction, performing extraction separation on an organic phase, washing with a saturated saline solution, drying with anhydrous sodium sulfate, and performing separation and purification through column chromatography, wherein a mole ratio of aromatic aldehyde to naphthenone is 1:(1-3); a mole ratio of aromatic aldehyde to the water is 1:(10-50); and the use level of catalyst is 1-5mol% of aromatic aldehyde. A synthesis technology of the calix [4] proline derivative is mild in condition and high in catalytic efficiency; the catalytic asymmetric Aldol reaction of the calix [4] proline derivative uses the water as the solvent and is green and environment-friendly; a good dr (anti/syn) value and a good ee (enantiomeric excess) value can be obtained by the catalytic reaction under a room temperature condition; and the calix [4] proline derivative has a wide application prospect.

Description

technical field [0001] The invention relates to the technical field of catalytic organic synthesis, in particular to a calix[4]proline derivative and a method for green catalytic asymmetric Aldol reaction thereof. Background technique [0002] The synthesis of carbon-carbon bonds is the most basic reaction in organic synthesis, and the Aldol reaction is one of the most effective means to construct carbon-carbon bonds. In recent years, with the continuous understanding and in-depth study of the concept of chirality, controlling the optical selectivity and diastereoselectivity of Aldol reactions has become an important research topic. At present, the asymmetric aldol reaction catalyzed by small organic molecules and metal complexes has been reported in a large number of literatures, but the catalysts used in the reaction still have some disadvantages, such as harmful to the environment, non-renewable, high toxicity, poor stability, low temperature reaction, etc. , and most of...

Claims

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Application Information

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IPC IPC(8): C07D207/16B01J31/02C07B53/00C07C205/45C07C201/12C07C255/56C07C253/30C07C49/747C07C49/753C07C45/73C07D213/50C07D309/30
Inventor 李正义韩辰马鸿钊孙小强
Owner 枣庄市新星钢结构有限公司
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