Trivalent cobalt Salen catalyst, synthesis method as well as application of trivalent cobalt Salen catalyst to resolution of terminal epoxides

A synthesis method and epoxide technology, which are used in the preparation of cobalt organic compounds, organic compounds, chemical instruments and methods, etc., can solve problems such as unfavorable large-scale industrial production, poor catalyst stability, and complex catalyst synthesis, and achieve excellent disassembly. The effect of splitting effect, good stability and high splitting efficiency

Active Publication Date: 2015-07-29
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Compared with catalyst 1, catalyst 2 has better activity, but the catalyst has poor stability, and the ester group structure in the catalyst is prone to hydrolysis and breakage during the reaction process
[0007] Since then, people have successively developed a variety of new multinuclear Salen catalysts, such as Catalyst 3 reported by Jones in 2010 (J. Hydrogen-bonded dinuclear catalyst 4 (Chem.Eur.J.2011,17,2236), but these catalysts are complicated to synthesize and expensive, which is not conducive to large-scale industrial production

Method used

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  • Trivalent cobalt Salen catalyst, synthesis method as well as application of trivalent cobalt Salen catalyst to resolution of terminal epoxides
  • Trivalent cobalt Salen catalyst, synthesis method as well as application of trivalent cobalt Salen catalyst to resolution of terminal epoxides
  • Trivalent cobalt Salen catalyst, synthesis method as well as application of trivalent cobalt Salen catalyst to resolution of terminal epoxides

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Trivalent cobalt Salen catalyst (I)-a (-O-A-O- is pyrocatechol ether, X is the synthetic steps of acetate):

[0045] (1) Preparation of compound (III)-a

[0046]

[0047]Under nitrogen protection, compound (III)-a (3.96g, 20mmol), sodium hydride (3.52g, 88mmol) and anhydrous tetrahydrofuran (20ml) were added to a 150ml dry three-necked flask, and stirred at 25°C for 1 hour. Compound (II) (9.07 g, 40 mmol) was dissolved in anhydrous tetrahydrofuran (50 ml), slowly dropped into the reaction flask, and stirring was continued for 20 hours after the drop was completed. After the reaction was stopped, most of the solvent was distilled off under reduced pressure, ethyl acetate (40ml) and 5% dilute hydrochloric acid (40ml) were added, the organic phase was separated, the aqueous phase was extracted three times with ethyl acetate, and the organic phase was combined with anhydrous sulfuric acid Dry over sodium, filter and concentrate, and the residue is separated by silica ge...

Embodiment 2

[0055] The synthetic steps of trivalent cobalt Salen catalyst (I)-b (-O-A-O- is 5-chloro-resorcinol ether, X is acetate):

[0056] (1) Preparation of compound (IV)-b

[0057]

[0058] Under nitrogen protection, compound (III)-b (3.96g, 20mmol), potassium tert-butoxide (11.20g, 100mmol) and anhydrous acetonitrile (20ml) were added to a 150ml dry three-necked flask, and stirred at 20°C for 2 hours . Compound (II) (9.07 g, 40 mmol) was dissolved in anhydrous acetonitrile (50 ml), slowly dropped into the reaction flask, and stirring was continued for 22 hours after the drop was completed. After the reaction was stopped, most of the solvent was distilled off under reduced pressure, ethyl acetate (40ml) and 5% dilute hydrochloric acid (40ml) were added, the organic phase was separated, the aqueous phase was extracted three times with ethyl acetate, and the organic phase was combined with anhydrous sulfuric acid Dry over sodium, filter and concentrate, and the residue is separat...

Embodiment 3

[0066] The synthetic steps of trivalent cobalt Salen catalyst (I)-c (-O-A-O- is hydroquinone ether, X is a trifluoromethanesulfonate radical):

[0067] (1) Preparation of compound (IV)-c

[0068]

[0069] Under nitrogen protection, compound (III)-c (3.96g, 20mmol), anhydrous potassium carbonate (12.42g, 90mmol) and anhydrous ether (20ml) were added to a 150ml dry three-necked flask, and stirred at 30°C for 2 hours . Compound (II) (9.07 g, 40 mmol) was dissolved in anhydrous diethyl ether (50 ml), slowly dropped into the reaction flask, and stirring was continued for 20 hours after the drop was completed. After the reaction was stopped, most of the solvent was distilled off under reduced pressure, ethyl acetate (40ml) and 5% dilute hydrochloric acid (40ml) were added, the organic phase was separated, the aqueous phase was extracted three times with ethyl acetate, and the organic phase was combined with anhydrous sulfuric acid It was dried over sodium, filtered and concentr...

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Abstract

The invention belongs to the technical field of organic chemistry, and particularly provides a trivalent cobalt Salen catalyst, a synthesis method of the trivalent cobalt Salen catalyst as well as an application of the trivalent cobalt Salen catalyst to resolution of terminal epoxides. The trivalent cobalt Salen catalyst is prepared from raw materials which are cheap and easy to obtain through simple reactions, is a binuclear macrocyclic catalyst, is used for catalyzing hydrolytic kinetic resolution of the terminal epoxides and is used at the temperature of 15-30 DEG C, the usage amount of the catalyst is 0.008-0.02 mol% of that of a racemization epoxide, the reaction yield can be higher than 48%, and the ee (enantiomeric excess) value of the resolution product is higher than 99%. The catalyst is mild in reaction condition, low in consumption, high in resolution efficiency and capable of being applied to hydrolytic kinetic resolution of the various terminal epoxides and has the high industrial application value.

Description

[0001] technology neighborhood [0002] The invention belongs to the technical field of organic chemistry, and in particular relates to a trivalent cobalt Salen catalyst, a synthesis method thereof and an application in splitting terminal epoxides. Background technique [0003] Salen is a general term for N,N'-ethylenebis(salicylimine) compounds. The chiral Salen complex is an important chiral catalyst and is widely used in asymmetric catalytic reactions, including the alkene Epoxidation and cyclopropanation, enantioselective epoxy ring opening, hydrolytic kinetic resolution, asymmetric heteroatom Diels-Alder reaction, asymmetric hydroxylation, selective hydrogenation, imine addition, etc. Chiral terminal epoxide is an important pharmaceutical intermediate. In recent years, the chiral drug industry has developed rapidly, and the synthesis and resolution of chiral terminal epoxide has gradually become a research hotspot. [0004] Jacobsen discloses in literature Science 1997,2...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07F15/06C07D303/08C07D303/04C07D303/40C07D301/32C07C31/42C07C31/20C07C29/10C07C69/675C07C67/31
Inventor 陈芬儿姚进熊方均吴妍陶媛万正勇
Owner FUDAN UNIV
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