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

Chiral tridentate nitrogen-nitrogen-phosphine ligand and application thereof in asymmetric hydrogenation reaction of ketone

A technology of tridentate nitrogen-nitrogen and phosphine ligands, used in catalytic reactions, organic compound/hydride/coordination complex catalysts, organic chemistry, etc. Ease of use, high reactivity, mild reaction conditions

Pending Publication Date: 2022-06-21
GUANGDONG UNIV OF TECH
View PDF8 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Inspired by Zhou Qilin's research group, in 2013, Zhang Shengyong's research group designed a series of tridentate PNN ligands containing ferrocene chirality, and found that such ligands have a good catalytic effect on the asymmetric hydrogenation of simple ketones. Unfortunately, The highest enantioselectivity can only reach 86% ee value (Tetrahedron:Asymmetry.2013,24,1567.; Organometallics.2014,33,2109.)

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 tridentate nitrogen-nitrogen-phosphine ligand and application thereof in asymmetric hydrogenation reaction of ketone
  • Chiral tridentate nitrogen-nitrogen-phosphine ligand and application thereof in asymmetric hydrogenation reaction of ketone
  • Chiral tridentate nitrogen-nitrogen-phosphine ligand and application thereof in asymmetric hydrogenation reaction of ketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Example 1: Synthesis of Ligand L1

[0045]

[0046] p-Toluenesulfonyl chloride (25.17g, 132mmol) and pyridine (12mL) were added to a 250mL flask, L-alaninol (4.51g, 60mmol) and pyridine (4mL) were added to the dropping funnel, and slowly added dropwise to the system , and stirred at room temperature for 16 h. Acetic acid (6 mL), ice (60 g), and water (120 mL) were added to quench the reaction, ethyl acetate was added, and 2M aqueous hydrochloric acid was added to the system to neutralize pyridine until no more pyridine remained, extracted with ethyl acetate, and the organic phases were combined. , washed with saturated brine, dried over anhydrous sodium sulfate, evaporated to remove the solvent, and recrystallized with n-hexane and ethyl acetate to obtain 17.46 g of a pale yellow solid with a yield of 76%.

[0047]

[0048] Compound 8 (11.50 g, 30 mmol) was dissolved in toluene (120 mL), 20% KOH aqueous solution (180 mmol, 50.5 g solution) was added dropwise, and...

Embodiment 2

[0057] Example 2: Synthesis of Ligand L4

[0058]

[0059] p-Toluenesulfonyl chloride (25.17 g, 132 mmol) and pyridine (12 mL) were added to a 250 mL flask, D-valinol 14 (6.19 g, 60 mmol) and pyridine (4 mL) were added to the dropping funnel, and slowly added dropwise The system was stirred at room temperature for 16h. Acetic acid (6 mL) was added, ice water (120 mL) was added to quench the reaction, ethyl acetate was added, and 2M aqueous hydrochloric acid was added to the system to neutralize pyridine until there was no pyridine residue, extracted with ethyl acetate, the organic phases were combined, and saturated brine Washed, dried over anhydrous sodium sulfate, evaporated to remove the solvent, and recrystallized with n-hexane and ethyl acetate to obtain 18 g of a pale yellow solid with a yield of 73%.

[0060]

[0061] Compound 15 (12.35 g, 30 mmol) was dissolved in toluene (120 mL), 20% KOH aqueous solution (180 mmol, 50.5 g solution) was added dropwise, and the ...

Embodiment 3

[0066] Example 3: Synthesis of Ligand L9

[0067]

[0068]Compounds 13 (228 mg, 0.5 mmol) and 18 (242 mg, 1.0 mmol) were refluxed in anhydrous MeOH (2 mL) overnight under nitrogen atmosphere, and the solvent was evaporated in vacuo to give the crude product. After chromatography on a silica gel column using petroleum ether / ethyl acetate (v / v)=20:1 to 3:1 as an eluent, 169 mg of a yellow solid was obtained with a yield of 53%. 1 H NMR (600MHz, CDCl 3 )δ7.81-7.64(m,2H),7.53(ddd,J=9.6,4.9,2.2Hz,2H),7.43-7.34(m,3H),7.25-7.16(m,7H),5.57(s, 1H), 4.46(p, J=1.6Hz, 1H), 4.32(t, J=2.5Hz, 1H), 4.05(dd, J=6.6, 2.8Hz, 1H), 4.00(s, 5H), 3.83( dt, J=2.4, 1.1Hz, 1H), 2.41(s, 3H), 2.11(s, 2H), 1.42(d, J=6.5Hz, 3H), 0.72(s, 3H), 0.59(s, 3H) ). 13 C NMR (151MHz, CDCl 3 )δ142.37,140.92,139.92(d,J=10.1Hz),136.96(d,J=9.0Hz),135.00,134.86,132.65,132.53,129.29,129.15,128.47,128.43,128.15,128.29(d,128.90. ,J=24.6Hz),74.98(d,J=7.6Hz),71.42(d,J=5.0Hz),69.71,69.36(d,J=4.6Hz),69.14,57.05,55.23,50...

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 belongs to the technical field of asymmetric catalysis, and discloses a chiral tridentate nitrogen-nitrogen-phosphine ligand and application thereof in asymmetric hydrogenation reaction of ketone. The ligand has a structure as shown in a general formula (I), a general formula (II) or a general formula (III). A catalyst obtained through reaction of a transition metal complex and the chiral nitrogen-nitrogen-phosphine tridentate ligand can be applied to preparation of various chiral alcohols. The chiral nitrogen-nitrogen-phosphine tridentate ligand disclosed by the invention has the characteristics of easiness in synthesis, good stability and the like, one part of a chiral module of the ligand is derived from amino acid which is cheap and easy to obtain, steric hindrance and electrical property are easy to regulate and control, and asymmetric hydrogenation of various ketones can be realized.

Description

technical field [0001] The invention belongs to the technical field of asymmetric catalysis, in particular to a chiral tridentate nitrogen phosphine ligand and its application in the asymmetric hydrogenation reaction of ketones. Background technique [0002] Chirality is a ubiquitous phenomenon in nature. Chiral molecules are mirror-symmetrical molecules in chemistry that cannot overlap in structure. Due to the strong chiral recognition ability of living organisms, chiral drugs have received attention. Because chiral compounds with different configurations often exhibit different biological activities, there are significant differences. The "arrest" event that occurred in the 1960s can better illustrate this problem. Thalidomide in the R configuration has a central sedative effect, while thalidomide in the S configuration has a strong teratogenic effect, which also leads to The cause of tens of thousands of newborn deformities. [0003] Chiral secondary alcohols are an imp...

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): C07F17/02B01J31/24C07C29/145C07C33/22C07C33/20C07C33/46C07C41/26C07C43/23C07D213/30C07D333/16C07D307/42C07D307/80C07D233/22C07C33/26C07C67/31C07C69/732C07C69/734C07C33/48C07C33/30C07D317/54
CPCC07F17/02B01J31/2404C07C29/145C07C41/26C07D213/30C07D333/16C07D307/42C07D307/80C07D233/22C07C67/31C07D317/54C07B2200/07B01J2231/643B01J2531/827C07C33/22C07C33/20C07C33/46C07C43/23C07C33/26C07C69/732C07C69/734C07C33/483C07C33/30
Inventor 叶金星刘成玉张磊程瑞华马跃跃孙茂林
Owner GUANGDONG UNIV OF TECH
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