Eureka AIR delivers breakthrough ideas for toughest innovation challenges, trusted by R&D personnel around the world.

Phosphine ligand and its enantiomer or racemate and its preparation method

A technology of enantiomers and phosphine ligands, which is applied in the field of phosphine ligands or their enantiomers or their racemates and their preparation, and can solve the problems of insufficient number and types of ligands, single skeleton space structure, etc.

Active Publication Date: 2015-09-02
SUN YAT SEN UNIV
View PDF2 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, compared with BINAP-like bidentate phosphine ligands, the number and types of such ligands are insufficient, and the skeleton (mostly binaphthyls) and spatial structure are relatively single

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
  • Phosphine ligand and its enantiomer or racemate and its preparation method
  • Phosphine ligand and its enantiomer or racemate and its preparation method
  • Phosphine ligand and its enantiomer or racemate and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057] Example 1: To prepare (S)-[6,6'-((2R,5R)-2,5-hexanedioloxy)]-2-N,N-dimethylamino-2'-bicyclic Hexylphosphine-1,1'-biphenyl as an example

[0058]

[0059] Preparation of (2R,5R)-2,5-bis-[(2-iodo-3-nitro)phenoxy]hexane:

[0060] 2-iodo-3-nitrophenol (5.30g, 0.02mol) and potassium carbonate (5.60g, 0.04mol) were added to 60mL of N,N-dimethylformamide (DMF), and stirred down to the mixing system Add (2S,5S)-2,5-hexanediol bis-p-toluenesulfonate (4.27g, 0.01mol), heat at 55°C until the reaction is complete (TLC tracking), and distill off DMF under reduced pressure. residues in water and CH 2 Cl 2 Partition in the middle, separate the organic phase and use CH for the aqueous phase 2 Cl 2 The organic phases were extracted and combined, washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and purified by column chromatography to obtain 5.10 g of a yellow solid compound with a yield of 83%. 1 H NMR (CDCl 3...

Embodiment 2

[0075] Example 2: To prepare (R)-[6,6'-((2S,3S)-2,3-butanediol oxygen)]-2-N,N-dimethylamino-2'-bicyclic Hexylphosphine-1,1'-biphenyl as an example

[0076]

[0077] Preparation of (2S,3S)-2,3-bis-[(2-iodo-3-nitro)phenoxy]butane:

[0078] Add 2-iodo-3-nitrophenol (5.30g, 0.02mol) and potassium carbonate (5.60g, 0.04mol) to 60mL N, N-dimethylformamide (DMF), and add to the mixing system under stirring (2R,3R)-2,3-Butanediol bis-p-toluenesulfonate (3.98g, 0.01mol), heated at 80°C until the reaction was complete (TLC tracking), and distilled off DMF under reduced pressure, the residue in water and CH 2 Cl 2 Partition in the middle, separate the organic phase and use CH for the aqueous phase 2 Cl 2 Extracted, combined organic phases, washed with saturated brine, dried over anhydrous magnesium sulfate, removed the solvent under reduced pressure, and purified by column chromatography to obtain 3.68 g of a yellow solid compound with a yield of 63%. 1 H NMR (CDCl 3 , TMS, 300...

Embodiment 3

[0093] Example 3: (S)-[6,6'-((2R,5R)-2,5-hexanedioloxy)]-2-N,N-dimethylamino-2'-dicyclohexylphosphine - Application of 1,1'-biphenyl in the asymmetric Suzuki reaction.

[0094]

[0095] In the glove box, 2-diethylphosphite-1-bromonaphthalene, (1.0mmol, 1.0equiv), 2-methylboronic acid (1.5equiv), Pd 2 (dba) 3 (0.5mol%), ligand (S)-[6,6'-((2R,5R)-2,5-hexanedioloxy)]-2-N,N-dimethylamino-2'- Dicyclohexylphosphine-1,1'-biphenyl (1.2 mol%) and potassium phosphate (3 equiv) were placed in a 6 mL dry one-necked bottle, the bottle was closed, and stirred at room temperature for 48 hours.

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 discloses a phosphine ligand and an enantiomer or a racemic body thereof and preparation methods and applications thereof. The structural formulae of the phosphine ligand and the enantiomer or the racemic body are shown in the specifications; a phosphine ligand compound has a novel framework; complete transfer of planar chirality to axial chirality in a synthesis process is realized through a desymmetrization reaction; a synthesis method is simple and economical; during preparation of a chiral ligand, common complex chiral splitting processes are avoided; and an obtained chiral ligand has the advantages of high reaction activity, high enantioselectivity and the like in a model reaction, can be applied to catalytic reactions of a plurality of metals such as palladium, rhodium, nickel, copper, iridium, ruthenium, iron, cobalt, gold, platinum and the like, and can have a very good catalytic effect.

Description

technical field [0001] The invention belongs to the field of chemical catalysis, and specifically relates to a class of phosphine ligands or their enantiomers or their racemates and a preparation method thereof. Background technique [0002] In asymmetric reactions, the design and synthesis of chiral catalysts with high enantioselectivity and catalytic activity are key. The design and synthesis of chiral catalysts is actually mainly the design and synthesis of chiral ligands, because they play a decisive role in the reactivity and enantioselectivity in transition metal-catalyzed asymmetric reactions [Noyori, R.; Ohkuma, T.Angew.Chem.Int.Ed.2002, 41, 2008], it can be said that the development of asymmetric catalysts is mainly reflected in the development of chiral ligands. From the perspective of chiral elements, there are central chirality, planar chirality, axial chirality and spiral chirality, etc.; from the number of coordination atoms, they can be divided into single-de...

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): C07F9/655C07D321/00C07D321/12B01J31/24C07F9/40C07F9/6561C07D493/04C07F9/50C07D307/33
Inventor 邱立勤吴文浩
Owner SUN YAT SEN UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
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