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Chiral guanidine catalysts based on tartaric acid skeleton, preparation method and application thereof

A technology of catalyst and tartaric acid, which is applied in the preparation of carboxylic acid esters, chemical instruments and methods, and the preparation of organic compounds, etc., and can solve the problems of limited types of chiral guanidine

Inactive Publication Date: 2013-09-04
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In general, although many chiral guanidine catalysts have been developed, the types of chiral guanidines are still limited, and their catalytic properties have yet to be fully explored.

Method used

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  • Chiral guanidine catalysts based on tartaric acid skeleton, preparation method and application thereof
  • Chiral guanidine catalysts based on tartaric acid skeleton, preparation method and application thereof
  • Chiral guanidine catalysts based on tartaric acid skeleton, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0077]

[0078] Reagents and conditions: a) 2,2-dimethoxypropane, p-toluenesulfonic acid, benzene, reflux, 12h; b) bromobenzene, magnesium powder, tetrahydrofuran, reflux, 1.5h, yield 91% (two steps reaction); c) thionyl chloride, triethylamine, dichloromethane, reflux, 3h, yield 65%; d) sodium azide, N,N-dimethylformamide, 80°C, 72h, yield 77%; e) lithium aluminum tetrahydrogen, tetrahydrofuran, 0 ℃, 4h, yield 93%; f) carbon disulfide, pyridine, 60 ℃, yield 98%; g) substituted amine, cuprous chloride, potassium carbonate, tetrahydrofuran , 40°C, 4-30h, yield 87-95%.

[0079] 1. Synthesis of G1-1:

[0080] Under nitrogen atmosphere, add anhydrous benzene (148mL), L-diethyl tartrate (12.4g, 60mmol), 2,2-dimethoxypropane (9.4g, 11mL, 90mmol, 1.5 eq.), p-toluenesulfonic acid (0.12g). Warm up to reflux and react for 12h. Cool to room temperature, add NaHCO 3 (1.5 g) continued stirring for 30 min. Add water (100mL), separate the organic phase, extract the aqueous phase tw...

Embodiment 2

[0096]

[0097] Reagents and conditions: a) 2,2-dimethoxypropane, p-toluenesulfonic acid, benzene, reflux, 12h; b) 4-phenylbromobenzene, magnesium powder, tetrahydrofuran, reflux, 1.5h, yield 95 % (two-step reaction); c) thionyl chloride, triethylamine, dichloromethane, reflux, 3h; d) sodium azide, N,N-dimethylformamide, 80 ° C, 72h, yield 79 % (two-step reaction); e) lithium aluminum tetrahydrogen, tetrahydrofuran, 0 ℃, 4h, yield 84%; f) carbon disulfide, pyridine, 60 ℃, yield 99%; g) substituted amine, cuprous chloride, Potassium carbonate, tetrahydrofuran, 40°C, 15-48h, yield 71-85%.

[0098] 1. Synthesis of G2-1:

[0099] Under nitrogen atmosphere, add anhydrous benzene (148mL), L-diethyl tartrate (4.1g, 20mmol), 2,2-dimethoxypropane (3.1g, 3.7mL, 30mmol, 1.5 eq.), p-toluenesulfonic acid (0.03g). Warm up to reflux and react for 12h. Cool to room temperature, add NaHCO 3 (0.5g) and continue to stir for 30min. Add water (40mL), separate the organic phase, extract t...

Embodiment 3

[0113]

[0114] Reagents and conditions: a) cyclohexanone, p-toluenesulfonic acid, zinc chloride, benzene, reflux, 18h; b) bromobenzene, magnesium powder, tetrahydrofuran, reflux, 1.5h, yield 75% (two-step reaction) ; c) thionyl chloride, triethylamine, dichloromethane, reflux, 3h; d) sodium azide, N,N-dimethylformamide, 80℃, 72h, yield 71% (two-step reaction) ; e) lithium aluminum tetrahydride, tetrahydrofuran, 0 ℃, 4h, yield 84%; f) carbon disulfide, pyridine, 60 ℃, yield 83%; g) p-methylbenzylamine, cuprous chloride, potassium carbonate, Tetrahydrofuran, 40°C, 12h, yield 62%.

[0115] 1. Synthesis of G3-1:

[0116] Under nitrogen atmosphere, add anhydrous benzene (200mL), L-diethyl tartrate (11.5g, 56mmol), cyclohexanone (8.2g, 8.7mL, 84mmol, 1.5eq.), p-toluene Sulfonic acid (0.35g), zinc dichloride (0.35g). The temperature was raised to reflux, and the reaction was carried out for 18h. Cool to room temperature, add NaHCO 3 (1.4g) Stirring was continued for 30min. ...

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Abstract

The invention relates to a series of chiral guanidine catalysts based on a tartaric acid skeleton and a preparation method thereof, and asymmetric catalytic application thereof, and belongs to the field of a catalyst technology and preparation methods of catalysts. The chiral guanidine catalysts have a structure shown in a general formula I or II; the basic skeletons heptatomic ring and five-membered ring respectively contain guanidyl and ketal structure units; and alpha, alpha'- of guanidyl on the heptatomic ring are respectively connected with two aryl groups. The invention provides a method for preparing chiral guanidine of the tartaric acid skeleton from chiral thiourea based on the tartaric acid skeleton and amine under promotion of cuprous chloride. The reaction temperature is 40 DEG C; the reaction time is 4-72 hours; and the yield is 50-99%. The chiral thiourea is prepared from tartrate by the steps of condensation, grignard reaction, chloro, azidation and reduction into chiral diamine and reaction with carbon disulfide.

Description

technical field [0001] The invention relates to a chiral guanidine catalyst based on a tartaric acid skeleton, a preparation method thereof, and an application thereof in catalyzing the asymmetric α-hydroxylation reaction of β-dicarbonyl compounds. The invention belongs to the field of catalyst technology and its preparation method. Background technique [0002] Chirality is one of the essential properties of nature. Biomacromolecules, such as proteins, polysaccharides, nucleic acids and enzymes, which are the important basis of life activities, are almost all chiral, and these molecules often have important physiological functions in the body. In recent years, with the development of synthetic methods, more and more chiral compounds can be obtained by chemical synthesis. Asymmetric catalytic synthesis has become an important means of obtaining chiral substances, and is one of the key technologies that must be broken through in the industrial production of chiral drugs. T...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07D491/056C07C69/757C07C67/31
Inventor 王保民邹立伟穆宏芳张焕瑞曲景平
Owner DALIAN UNIV OF TECH
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