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

Axially unstable bipyridine-bisoxazoline chiral ligands and their preparation and application

A bisoxazoline and axially unstable technology, which is applied to axially unstable bipyridine-bisoxazoline chiral ligands and the fields of preparation and application thereof, can solve the waste of axially chiral ligands, and only has a central hand. Sexual and chiral ligands are expensive

Inactive Publication Date: 2015-10-14
SHANGHAI JIAOTONG UNIV
View PDF4 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, from the point of view of atom economy, the ligands designed in this way have two obvious limitations:
Whether by resolution or synthesis from optically pure chiral raw materials, the price of the obtained optically pure chiral ligands will be relatively expensive, and the development and application of chiral catalysts will be limited.
[0004] 2. For the axial chiral bisoxazoline ligands, when they coordinate with the metal, they form diastereoisomers. Only one of the two enantiomers of the neutral ligand can obtain a good asymmetric catalytic effect, so it is bound to cause a waste of the other enantiomer axis chiral ligand
[0006] However, the pyridine-oxazoline ligands reported in the prior art only have central chirality, and when they participate in asymmetric catalysis, the chirality of the product can only be induced by the central chirality of the ligand.

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
  • Axially unstable bipyridine-bisoxazoline chiral ligands and their preparation and application
  • Axially unstable bipyridine-bisoxazoline chiral ligands and their preparation and application
  • Axially unstable bipyridine-bisoxazoline chiral ligands and their preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Embodiment 1: the synthesis of bipyridyl-isopropyl oxazoline

[0026]

[0027] Under the condition of nitrogen protection, 2.72 g (0.01 mol) of methyl bipyridylcarboxylate and 4.12 g (0.04 mol) of s-isopropylamino alcohol were added to the system, heated to 120°C and stirred for 20 hours, then cooled to room temperature, Then add 30ml of dichloromethane, 5ml of thionyl chloride and reflux for 6 hours, then evaporate the solvent under reduced pressure, dissolve the obtained viscous substance in 15ml of methanol, add dropwise to 15ml of methanol solution of 2.6g of sodium hydroxide, and reflux for 6 hours. After one hour, the solvent was evaporated under reduced pressure, 50 ml of dichloromethane was added to dissolve, washed with saturated sodium carbonate solution and saturated sodium chloride solution, dried over anhydrous sodium sulfate, and passed through a column with petroleum ether / ethyl acetate 2:1 to obtain 1.93 g of a white solid , yield 51%.

[0028] 1 H ...

Embodiment 2

[0029] Embodiment 2: the synthesis of bipyridyl-phenyloxazoline

[0030]

[0031]Under the condition of nitrogen protection, add 2.72g (0.01mol) of methyl bipyridylcarboxylate and 5.49g (0.04mol) of s-phenylamino alcohol to the system, heat to 120°C and stir for 20 hours, then cool to room temperature, and then Add 30ml of dichloromethane, 5ml of thionyl chloride and reflux for 6 hours, then evaporate the solvent under reduced pressure, dissolve the obtained viscous substance in 15ml of methanol, add dropwise to 2.6g of sodium hydroxide in 15ml of methanol solution, and reflux for 6 hours After that, the solvent was evaporated under reduced pressure, 50 ml of dichloromethane was added to dissolve, washed with saturated sodium carbonate solution, saturated sodium chloride solution, dried over anhydrous sodium sulfate, and petroleum ether / ethyl acetate 2:1 was passed through the column to obtain 2.50 g of white solid. Yield 56%.

[0032] 1 H NMR (400MHz, CDCl 3 ): δ8.75(s,...

Embodiment 3

[0033] Embodiment 3: the synthesis of bipyridine-benzyl oxazoline

[0034]

[0035] Under the condition of nitrogen protection, 2.72g (0.01mol) of methyl bipyridylcarboxylate and 6.05g (0.04mol) of s-benzylamino alcohol were added to the system, heated to 120°C and stirred for 20 hours, cooled to room temperature, and then Add 30ml of dichloromethane, 5ml of thionyl chloride and reflux for 6 hours, then evaporate the solvent under reduced pressure, dissolve the obtained viscous substance in 15ml of methanol, add dropwise to 2.6g of sodium hydroxide in 15ml of methanol solution, and reflux for 6 hours Afterwards, the solvent was evaporated under reduced pressure, and 50 ml of dichloromethane was added to dissolve, washed with saturated sodium carbonate solution and saturated sodium chloride solution, dried over anhydrous sodium sulfate, and passed through a column with petroleum ether / ethyl acetate 2:1 to obtain 2.94 g of a white solid. Yield 62%.

[0036] 1 H NMR (400MHz,...

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 provides an axis-unfixed bipyridyl-bis-oxazoline chiral ligand in the technical field of catalysts, and the preparation and the application thereof. The structural formula of the ligand is figured. The invention has the advantages as follows: the method is simple, the yield is higher, and the prepared ligand is coordinated with palladium, copper, silver and zinc, thereby having a fine application prospect in lots of catalytic reactions.

Description

technical field [0001] The invention relates to a ligand in the technical field of catalysts and a synthesis method thereof, in particular to an axis-unstable bipyridine-bisoxazoline chiral ligand and its preparation and application. Background technique [0002] Since the successful application of the axis-stabilizing chiral ligand BINAP, a large number of axis-stabilizing chiral ligands (Atropos ligands) have been reported in the past 20 years. The optically pure axial chiral ligand with a single axial chiral configuration is coordinated with a metal to obtain a corresponding metal coordination compound with stable axial chirality, that is, an axial chiral asymmetric catalyst, and it is applied to asymmetric catalysis. However, from the point of view of atom economy, the ligands designed in this way have two obvious limitations: [0003] 1. It is difficult to obtain optically pure axial chiral ligands. There are two main methods for preparing optically pure axial chiral ...

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 Patents(China)
IPC IPC(8): C07D413/14B01J31/22
Inventor 张万斌江峰吴正兴
Owner SHANGHAI JIAOTONG 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