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

Chiral bidentate nitrogen phosphine ligand Rong-Phos as well as preparation method and application thereof

A bidentate nitrogen and phosphine ligand technology, applied in organic chemistry methods, chemical instruments and methods, catalytic reactions, etc., can solve the problem that the chirality of the nitrogen atom is easy to flip and unstable, the influence and effect of the nitrogen atom center have not been studied, and the chiral Problems such as sexuality are not considered by people, and achieve the effect of many modifiable sites, excellent reactivity and high enantioselectivity, and simple ligand structure

Active Publication Date: 2020-07-10
EAST CHINA NORMAL UNIV
View PDF3 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The chiral centers commonly used in chiral ligands are carbon chiral centers, phosphorus chiral centers, and sulfur chiral centers, because they are stable, and when sp 3 When a hybrid nitrogen atom connects three different groups, the nitrogen atom can also become a chiral center, but the chirality of the nitrogen atom is easy to flip and is very unstable, so that its chirality is usually not considered by people, so the nitrogen atom also Not used as chiral centers to design corresponding chiral ligands
Although some nitrogen-containing chiral ligands have been reported, the influence and effect of the chirality at the nitrogen center in asymmetric catalytic reactions has not been investigated.

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 bidentate nitrogen phosphine ligand Rong-Phos as well as preparation method and application thereof
  • Chiral bidentate nitrogen phosphine ligand Rong-Phos as well as preparation method and application thereof
  • Chiral bidentate nitrogen phosphine ligand Rong-Phos as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0099] Example 1 (S C , R S )-6a synthesis

[0100] Refer to method 1, in a 50mL dry single-mouth bottle, add under helium atmosphere (1mmol) and dry tetrahydrofuran solvent (10mL), stirred at -40°C for 10 minutes, and added n-butyllithium (1.6eq., 1mL, 1.6M) dropwise. Stirring was continued for 1 hour, methyl triflate (1.6 mmol) was added, followed by stirring for 30 minutes. The reaction was then quenched with saturated ammonium chloride solution. Separation, extraction, drying, spin-drying solvent and column chromatography purification were carried out again to obtain The yield was 91%. Proton NMR (500MHz, Chloroform-d) δ7.76–7.69(m,1H),7.37–7.21(m,11H),7.18–7.11(m,1H),7.11–7.04(m,1H),5.43( d, J=13.6Hz, 1H), 2.62(s, 3H), 1.13(s, 9H), 1.01(s, 9H). Phosphorus NMR (202MHz, CDCl 3 )δ-16.37. Carbon NMR (126MHz, Chloroform-d) δ145.99(d, J=24.4Hz), 137.31(d, J=10.6Hz), 137.08(d, J=2.7Hz), 136.99(d ,J=3.4Hz),135.39,133.92(d,J=6.9Hz),133.76(d,J=7.1Hz),129.57(d,J=3.6Hz),1...

Embodiment 2

[0101] Example 2 (S C , R S )-6b synthesis

[0102] Concrete operation with reference to embodiment 1, used raw material is The yield was 86%. Proton NMR (500MHz, Chloroform-d) δ7.76–7.71(m,1H),7.43–7.39(m,1H),7.35–7.29(m,9H),7.28–7.23(m,3H),5.47( d, J=13.1Hz, 1H), 2.84(s, 3H), 1.88–1.73(m, 6H), 1.63–1.48(m, 9H), 1.08(s, 9H). Phosphorus NMR (202MHz, CDCl 3 )δ-18.14, carbon NMR (126MHz, Chloroform-d) δ143.89(d, J=25.9Hz), 137.80(d, J=11.9Hz), 137.33(d, J=12.3Hz), 137.15(d ,J=10.8Hz),136.16(d,J=1.8Hz),134.10(d,J=20.0Hz),133.45(d,J=19.0Hz),129.98(d,J=4.1Hz),128.67,128.51 –128.37(m), 128.33, 127.14, 73.65(d, J=27.5Hz), 58.66, 40.68(d, J=1.6Hz), 40.04, 30.10(d, J=1.4Hz), 28.62, 24.75(d, J=2.0Hz). High resolution mass spectrometry theoretical data C 34 h 43 NOPS([M+H] + ), 544.2797, experimental data 544.2794.

Embodiment 3

[0103] Example 3 (S C , R S )-6c synthesis

[0104] Concrete operation with reference to embodiment 1, used raw material is The yield was 76%. Proton NMR (500MHz, Chloroform-d) δ7.52–7.12(m,14H),5.23(t,J=10.2Hz,1H),2.64(s,3H),2.15–2.03(m,1H),2.00 –1.88(m,1H),1.84–1.75(m,1H),1.61–1.50(m,1H),1.40–1.27(m,2H),1.22–0.91(m,13H),0.85–0.78(m, 1H). Phosphorus NMR (202MHz, CDCl 3 )δ-18.64. Carbon NMR (126MHz, Chloroform-d) δ145.32(d, J=25.4Hz), 137.04(d, J=12.1Hz), 136.80–136.51(m), 135.02, 134.53(d, J=20.7Hz), 133.57(d, J=18.8Hz), 129.16, 128.89, 128.66–128.32(m), 127.15, 126.86(d, J=4.9Hz), 70.10(d, J=26.3Hz), 58.61 C 30 h 38 NNaOPS([M+Na] + ), 514.2304, experimental data 514.2297.

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 novel chiral bidentate nitrogen phosphine ligand Rong-Phos as shown in a formula (1), and a preparation method and application thereof. The invention also discloses a chiralbidentate nitrogen phosphine ligand Rong-Phos iridium complex shown as a formula (2) and a nitrogen chiral center high-enantioselectivity construction method and application thereof. The iridium complex has a carbon chiral center and a nitrogen chiral center at the same time and is stable in property; a method for constructing the nitrogen atom center of the iridium complex by adopting high enantioselectivity is used, and a pair of diastereoisomer catalysts with different nitrogen center chirality of the iridium complex is applied to asymmetric hydrogenation reaction of a cyclic unsaturated carbonyl compound; the iridium complex also has excellent reaction activity and enantioselectivity in asymmetric hydrogenation reaction of other cyclic unsaturated carbonyl compounds, the effect is remarkable and excellent, and the iridium complex has scientific research value and wide application prospect.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and specifically relates to a novel chiral bidentate nitrogen phosphine ligand and its preparation and application. Background technique [0002] Chirality exists widely in nature. Chiral compounds are just like people's left and right hands, which cannot overlap each other. Two enantiomers are mirror images of each other but cannot be completely overlapped. Seemingly similar two enantiomers often have different optical properties, physicochemical properties and different or even opposite biological activities. [0003] In 2001, the Nobel Prize in Chemistry was awarded to Knowles, Noyori and Sharpless for their research on asymmetric catalytic hydrogenation and asymmetric catalytic oxidation. Asymmetric hydrogenation has become one of the most effective methods for preparing various optically pure compounds because of its high efficiency, atom economy and good industrial application pr...

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): C07F9/50C07F15/00B01J31/24B01J31/22C07D207/267C07D207/26C07D211/76C07D211/86C07D223/10
CPCB01J31/2295B01J31/2404B01J2231/645B01J2531/0225B01J2531/0238B01J2531/0261B01J2531/827C07B2200/07C07D207/26C07D207/267C07D211/76C07D211/86C07D223/10C07F9/5022C07F15/0033
Inventor 张俊良张荣华徐杉
Owner EAST CHINA NORMAL 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