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

Chiral macrocyclic aminophosphine ligand, and preparation method and application thereof

A technology of phosphine ligands and macrocyclic amines, which is applied in the field of chiral macrocyclic phosphine amine ligands and its preparation, can solve the problems of low optical purity, improve enantioselectivity, improve stability and rigidity, and facilitate operation Effect

Inactive Publication Date: 2011-06-15
XIAMEN UNIV
View PDF2 Cites 2 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But the optical purity of the corresponding chiral alcohol is very low, only 11%-30%ee

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
  • Chiral macrocyclic aminophosphine ligand, and preparation method and application thereof
  • Chiral macrocyclic aminophosphine ligand, and preparation method and application thereof
  • Chiral macrocyclic aminophosphine ligand, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: Chiral cyclic P 2 N 4 Preparation of type imidophosphine ligand (compound (R, R, R', R')-2)

[0031] The chiral ring P is given by 2 N 4 The synthetic route of type imidophosphine ligand (compound (R, R, R', R')-2):

[0032]

[0033] Bis(2-formylphenyl)phenylphosphine (9.55 g, 0.03 mol) and (R,R)-1,2-cyclohexanediamine (3.43 g, 0.03 mol) were added to a 400 mL round bottom flask, Chloroform (300 mL) was added under a nitrogen atmosphere, the reaction was stirred, and the temperature was rapidly raised to 40°C. After 3h, anhydrous sodium sulfate (60g) was added and reacted at 40°C for 24h. Cool to room temperature under nitrogen. Remove sodium sulfate by filtration, wash twice with saturated ammonium chloride aqueous solution (100mL×2), then dry over anhydrous sodium sulfate, filter, evaporate the solvent under reduced pressure, and recrystallize with chloroform and n-hexane to obtain yellow-green crystals (11.2 g). According to X-ray single crystal...

Embodiment 2

[0038] Example 2: Chiral cyclic P 2 (NH) 4 Preparation of Type Aminophosphine Ligand (Compound (R, R, R', R')-3)

[0039] The chiral ring P is given by 2 (NH) 4 The synthetic route of type amine phosphine ligand (compound (R, R, R', R')-3):

[0040]

[0041] (R, R, R', R')-2 (1.0g, 1.3mmol) and NaBH 4 (1.0g, 26.3mmol) was added into a 150mL three-necked flask, and ethanol (50mL) was added under a nitrogen atmosphere, the temperature was raised to 40°C, and the reaction was stirred at this temperature for 12h to stop the reaction. After cooling to room temperature with nitrogen gas, it was extracted with dichloromethane (150 mL), and washed with distilled water (total 120 mL×3). It was then dried over anhydrous sodium sulfate, filtered, evaporated to remove the solvent under reduced pressure, and dried in vacuo to obtain milky white solid (R, R, R', R')-3 (0.80 g, yield 80%). Melting point: 191-193°C. 1 H NMR (400MHz, CDCl 3 ): δ0.80-0.96(m, 2H), 0.98-1.39(m, 6H), 1....

Embodiment 3

[0047] Compound (R, R, R', R')-3 is used as a chiral ligand for asymmetric catalytic hydrogenation of ketones

[0048]

[0049] (R, R, R', R')-3 (8.0mg, 0.01mmol), RhH(CO)(PPh 3 ) 3 (9.2mg, 0.01mmol) and NH 4 I (22.0mg, 0.15mmol) was added to the reaction tube, 20ml of isopropanol was added in the air, and after stirring at room temperature for 30min, 0.2M KOH / i PrOH solution (115ml, 0.23mmol), stirring was continued for 10min, then acetophenone (0.234ml, 2.0mmol) was added. That is, the mol ratio of each material added is ketone: Rh: ligand: NH 4I:KOH=200:1:1:15:23. The mixed solution was stirred and reacted at 65° C. for 3 h. The reaction solution was analyzed by gas chromatography (chiral chromatographic column: CP-Cyclodextrin-β-2,3,6-M-19, 50m), and the chemical yield and optical purity of the product (S)-phenethyl alcohol were respectively 97% and 86% 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 chiral macrocyclic aminophosphine ligand, in particular to a chiral macrocyclic aminophosphine ligand, and a preparation method and application thereof. (R,R,R',R')-2 is prepared by reacting di(2-formacylphenyl)phenylphosphine with (R,R)-cyclohexyl-1,2-diamine in the presence of a halogenated hydrocarbon and a dehydrating agent. (R,R,R',R')-3 is prepared by reacting the(R,R,R',R')-2 with NaBH4 in a solvent. (S,S,S',S')-4 is prepared by reacting the di(2-formacylphenyl)phenylphosphine with (S,S)-cyclohexyl-1,2-diamine in the presence of a halogenated hydrocarbon anda dehydrating agent. (S,S,S',S')-5 is prepared by reacting (S,S,S',S')-4 with NaBH4 in a solvent. The chiral cyclic aminophosphine ligand can be used for preparing catalysts of chiral aromatic alcohols.

Description

technical field [0001] The invention relates to a chiral macrocyclic phosphine amine ligand, in particular to a chiral macrocyclic phosphine amine ligand used in the field of asymmetric catalytic synthesis, a preparation method and application thereof. Background technique [0002] Since the two isomers [(R)-isomer and (S)-isomer] in the chiral drug molecule have different molecular recognition in the organism, there are significant differences in their pharmacological activity, metabolic process and toxicity , or even on the contrary, so how to obtain a single enantiomerically pure compound is a great challenge to chemists and the pharmaceutical industry. [0003] Asymmetric catalytic synthesis is one of the most efficient and important ways to prepare single enantiomer compounds. It only uses a small amount of chiral catalyst to generate a large amount of optically active products. Chiral catalysts usually consist of a metal center and a chiral ligand. The metal center e...

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
IPC IPC(8): C07F9/50C07C33/22C07C29/143C07C33/34C07C33/46C07D333/16
Inventor 高景星沈伟艺李岩云董振荣余神銮
Owner XIAMEN UNIV
Features
  • Generate Ideas
  • Intellectual Property
  • Life Sciences
  • Materials
  • Tech Scout
Why Patsnap Eureka
  • Unparalleled Data Quality
  • Higher Quality Content
  • 60% Fewer Hallucinations
Social media
Patsnap Eureka Blog
Learn More

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

© 2025 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com