Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Method for asymmetrically synthesizing dihydrofuran-2-(3H)-one compound under catalysis of nickel

A technology of ketone compounds and dihydrofuran, applied in organic chemistry methods, organic chemistry, etc., can solve the problems of unfriendly environment, high cost, high toxicity, etc., achieve high yield and enantioselectivity, low cost, The effect of easy operation

Pending Publication Date: 2021-08-06
YUNNAN MINZU UNIV
View PDF1 Cites 5 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the synthesis of dihydrofuran-2-(3H)-one compounds is mainly catalyzed by transition noble metals. This method is costly, highly toxic and unfriendly to the environment.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for asymmetrically synthesizing dihydrofuran-2-(3H)-one compound under catalysis of nickel
  • Method for asymmetrically synthesizing dihydrofuran-2-(3H)-one compound under catalysis of nickel
  • Method for asymmetrically synthesizing dihydrofuran-2-(3H)-one compound under catalysis of nickel

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041]

[0042] In the glove box, add accurately weighed 0.01 mmol of nickel acetate tetrahydrate and 0.012 mmol of the ligand into a Schneck reaction tube with a stirring bar, add 1 mL of 1,4-dioxane, and plug the rubber stopper Stir at room temperature for 30 min, then add 0.2 mmol of the substrate 3-benzoylpropionic acid, zinc trifluoromethanesulfonate (0.02 mmol) and 1 mL of 1,4-dioxane. Take out the reaction tube and put it into an autoclave, replace the hydrogen 3 times, the hydrogen pressure is 3 Mpa, set the temperature at 70°C under the oil bath, and wait until the reaction is complete. After the reaction was completed, the reaction tube was taken out, and the reaction liquid was removed under reduced pressure using a rotary evaporator to remove volatile solvents, and ethyl acetate / petroleum ether was used as an eluent, and purified by column chromatography to obtain the product. (96% yield, 94% ee). 1 H NMR (400MHz, CDCl 3 ) δ 7.49 – 7.30 (m, 5H), 5.58 – 5.46 (m...

Embodiment 2

[0044]

[0045] In the glove box, add accurately weighed 0.01 mmol of nickel acetate tetrahydrate and 0.012 mmol of the ligand into a Schneck reaction tube with a stirring bar, add 1 mL of 1,4-dioxane, and plug the rubber stopper Stir at room temperature for 30 min, then add 0.2 mmol of the substrate 3-benzoylpropionic acid, zinc trifluoromethanesulfonate (0.02 mmol) and 1 mL of 1,4-dioxane. Take out the reaction tube and put it into an autoclave, replace the hydrogen 3 times, the hydrogen pressure is 3 Mpa, set the temperature at 50°C under the oil bath, and wait until the reaction is complete. After the reaction was over, the reaction tube was taken out, and the reaction solution used a rotary evaporator to remove the volatile solvent under reduced pressure, and used ethyl acetate / petroleum ether as eluent, and purified by column chromatography to obtain the product (88% yield, 94% ee).

Embodiment 3

[0047]

[0048] In the glove box, add accurately weighed 0.01 mmol of nickel acetate tetrahydrate and 0.012 mmol of the ligand into a Schneck reaction tube with a stirring bar, add 1 mL of 1,4-dioxane, and plug the rubber stopper Stir at room temperature for 30 min, then add 0.2 mmol of the substrate 3-benzoylpropionic acid, zinc trifluoromethanesulfonate (0.02 mmol) and 1 mL of 1,4-dioxane. Take out the reaction tube and put it into an autoclave, replace the hydrogen 3 times, the hydrogen pressure is 3 Mpa, set the temperature at 90°C under the oil bath, and wait until the reaction is complete. After the reaction was over, the reaction tube was taken out, and the reaction solution used a rotary evaporator to remove the volatile solvent under reduced pressure, and used ethyl acetate / petroleum ether as eluent, purified by column chromatography to obtain the product (88% yield, 92% ee).

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a method for asymmetrically synthesizing a dihydrofuran-2-(3H)-one compound under the catalysis of nickel, wherein the method comprises the steps: by taking gamma-ketonic acid as a raw material, adding a nickel catalyst, a ligand and Lewis acid in an organic solvent environment in which hydrogen is taken as a hydrogen source at the pressure of 0.1-6 MPa and the temperature of 50-90 DEG C, and carrying out hydrogenation reaction to synthesize the dihydrofuran-2-(3H)-one compound. By adopting a transition metal-lewis acid synergistic catalysis strategy and taking nickel acetate tetrahydrate as a transition metal catalyst, the preparation method has the advantages of easiness in obtaining and low cost; zinc trifluoromethanesulfonate is added, so that the reaction temperature is greatly reduced from 150 DEG C to 70 DEG C, and compared with a metal catalytic reaction in the prior art, the reaction is milder. The method disclosed by the invention is wide (suitable) in application range, simple in catalytic system, simple and convenient to operate and high in yield and enantioselectivity (the yield is as high as 97%, and ee is as high as 95%), the production cost is greatly reduced, and the method has remarkable social benefits and economic benefits.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a nickel-catalyzed asymmetric synthesis method of dihydrofuran 2-(3H)-ketone compounds. Background technique [0002] Asymmetric hydrogenation catalyzed by transition metals is one of the fundamental reactions in the organic synthesis industry, which has been widely used due to its high efficiency in the preparation of optically pure compounds. [0003] The asymmetric hydrogenation of ketones provides an efficient route with 100% atomic efficiency for the synthesis of chiral alcohols. Organoketones are an important class of carbonyl-containing compounds with potential applications in materials science and synthetic organic chemistry. Its reductive hydrogenation has a wide range in the field of organic research, and common researchers mainly focus on metal catalysis and metal-nonmetal synergistic catalysis. However, most metal catalysis technologies involv...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/33
CPCC07D307/33C07B2200/07
Inventor 周永云陈景超樊保敏和振秀樊瑞峰孙蔚青张科阳
Owner YUNNAN MINZU UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com