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Ion group modified 4,4'-bit chiral oxazoline ligand and synthesis method thereof

A bisoxazoline and ionic group technology, applied in the field of asymmetric synthesis, can solve the problems of ligand toxicity, high cost, high economic cost, etc., and achieve the effect of good enantioselectivity, high catalytic activity and simple circuit

Inactive Publication Date: 2013-09-25
福建省北理展华医药技术研发有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] However, in order to meet the development of the chemical industry and the production requirements of green chemical industry, today's asymmetric catalysis research still faces many challenges.
In most catalytic reactions, the amount of chiral catalyst is 5mol% to 10mol%, and the high economic cost and complicated separation process cannot meet the requirements of large-scale production
Especially for asymmetric reactions catalyzed by chiral metal complexes, the ligand itself has unpredictable toxicity, which may cause great harm to human health and ecological balance, and these ligands and metals have greater cost problems. Difficulty in recycling also limits its industrial production

Method used

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  • Ion group modified 4,4'-bit chiral oxazoline ligand and synthesis method thereof
  • Ion group modified 4,4'-bit chiral oxazoline ligand and synthesis method thereof
  • Ion group modified 4,4'-bit chiral oxazoline ligand and synthesis method thereof

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Effect test

Embodiment 1

[0025] The synthetic method of ionic group modification 4,4' chiral bisoxazoline ligand comprises the following steps:

[0026] (1) Synthesis of Dimethylmalonyl Chloride

[0027] Under the protection of an inert gas, dissolve dimethylmalonic acid (0.75g, 5.68mmol) in anhydrous dichloromethane (10mL), add a small amount of DMF (0.74mmol, 0.13eq) as a catalyst, and cool to 0°C in an ice-water bath , Dissolve oxalyl chloride (17mmol, 3.0eq) after distillation and purification in 5mL of anhydrous dichloromethane and store in a constant pressure dropping funnel, add the dichloromethane solution of oxalyl chloride dropwise very slowly, after the addition is complete, the reaction solution Slightly pale yellow, naturally heated up, and reacted at room temperature for 18h. After the reaction was completed, the solvent was evaporated to dryness, and distillation under reduced pressure (52°C fraction was collected) gave a colorless liquid, yield: 0.82g (86%). 1 H NMR (400MHz, CDCl 3 ...

Embodiment 2

[0041] The synthetic method of ionic group modification 4,4' chiral bisoxazoline ligand comprises the following steps:

[0042] (1) By the method of steps (1), (2), (3), (4), (5) in Example 1, the bisoxazoline substituted by p-toluenesulfonate was prepared.

[0043] (2) Synthesis of iodine-substituted bisoxazolines

[0044] Under the protection of an inert gas, dissolve the bisoxazoline (0.516g, 0.9mmol) substituted by p-toluenesulfonate in 15mL of anhydrous acetone, add a large excess of sodium iodide (2.7g, 10.0eq), after fully dissolving The oil bath was heated to reflux and reacted overnight. After the reaction, cool to room temperature naturally, add saturated sodium bicarbonate solution to wash away excess sodium iodide, add anhydrous ether to dissolve the product, extract and separate the liquid, dry the organic phase with anhydrous sodium sulfate, and concentrate to obtain a crude product. Purified by silica gel column chromatography (PE / EtOAc 1:1) to obtain 276 mg o...

Embodiment 3

[0048] Asymmetric Henry reaction catalyzed by bisoxazoline ligands with p-toluenesulfonate anions: Under argon protection, bisoxazoline ligands with p-toluenesulfonate anions (2.5 mg, 3.3 μmol) and copper acetate Cu (OAc)2 ·H 2 O (0.7 mg, 3.3 μmol) was dissolved in anhydrous methanol (1 mL), reacted at room temperature for 2 h, added substrate p-nitrobenzaldehyde (0.34 mmol) to the solution to adjust to 25 ° C, and added nitromethane (6.8 mmol), after reacting for 48 hours, the solvent was dried under reduced pressure, and the crude product was subjected to column chromatography (ethyl acetate / petroleum ether, 3:7) to obtain the final product with a yield of 86%. The enantiomeric excess value (ee value) of the product was analyzed by HPLC. Conditions: chiralcel OD-H, n-hexane:isopropanol=85:15, 0.8mL / min, and the ee value was 58%.

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Abstract

The invention discloses a structure and synthesis method of an ion group modified 4,4'-bit chiral oxazoline ligand. The synthesis method is low in cost, simple in process, high in yield, and small in environment pollution. The invention also discloses an application and an application method of the ion group modified 4,4'-bit chiral oxazoline ligand in asymmetric Henry reactions; the ion group modified 4,4'-bit chiral oxazoline ligand is applied to an asymmetric Henry reaction so as to achieve high antipodal selectivity, and has a good recovery performance, therefore, the ion group modified 4,4'-bit chiral oxazoline ligand is an economical, efficient and environmentally-friendly novel chiral ligand.

Description

technical field [0001] The present invention relates to ionic group modified 4,4'-position chiral bisoxazoline ligand and its synthesis method, and ion group-modified 4,4'-position chiral bisoxazoline ligand in asymmetric Henry reaction The invention belongs to the technical field of asymmetric synthesis. Background technique [0002] So far, oxazoline, as one of the most widely used ligands, has received extensive attention and in-depth research from many chemists. Chiral bisoxazoline ligands have been shown to be applicable to a variety of asymmetric catalytic reactions. The chiral bisoxazoline ligand-metal system has high stability, good catalytic performance, and a wide range of applications. It also represents the development direction of asymmetric catalysis. [0003] However, in order to meet the development of chemical industry and the production requirements of green chemical industry, today's asymmetric catalysis research still faces many challenges. In most cat...

Claims

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Application Information

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IPC IPC(8): C07D413/14B01J31/22C07C201/12C07C205/19C07C205/32C07C205/16
Inventor 周智明刘应强李志怀戴力
Owner 福建省北理展华医药技术研发有限公司
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