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

Chiral tertiary phosphine compound, full configuration, preparation method and application thereof

A compound, chiral phosphine technology, applied in chiral tertiary phosphine compound and its full configuration, its preparation and application fields, can solve the problems of expensive raw materials, low overall yield, long synthetic route, etc., and achieve easy transformation, raw material Inexpensive, highly selective effect

Active Publication Date: 2015-08-05
苏州凯若利新材料科技有限公司
View PDF3 Cites 5 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method not only has long steps and low overall yield, but also has great difficulties in synthesizing all configurational isomers, which needs to be based on raw materials with different chiral configurations
The synthesis of phosphine-containing compounds in the prior art has defects such as relatively expensive raw materials, long synthetic routes, low yields, and long reaction times.

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 tertiary phosphine compound, full configuration, preparation method and application thereof
  • Chiral tertiary phosphine compound, full configuration, preparation method and application thereof
  • Chiral tertiary phosphine compound, full configuration, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] (S)-N-((R S )-2-(diphenylphosphino)-1-phenylethyl)-2-methylpropane-2-sulfinamide[1a(S,R S )]Synthesis

[0041]

[0042] Wherein, THF is tetrahydrofuran; N 2 is nitrogen; Ti( i PrO) 4 For tetraisopropyl titanate.

[0043] Step 1: In a 500mL three-necked flask, add benzaldehyde (50mmol) and (R)-(+)-tert-butylsulfinamide (50mmol), add 150mL tetrahydrofuran under nitrogen atmosphere, add tetratitanate Isopropyl ester (100mmol), stirred at 50°C for 10h, the yield was 85%.

[0044]

[0045] The second step: add the imine (1.04 g, 5 mmol) prepared in the first step into a 50 mL eggplant-shaped reaction flask, protect with nitrogen, and add 30 mL of tetrahydrofuran. Lithium diphenylmethylenephosphine (10 mmol) was slowly added at room temperature, stirred overnight, and the yield was 71%. Proton NMR (400MHz, CDCl 3 )δ7.45-7.41(m,2H),7.36-7.28(m,7H),7.27-7.25(m,6H),4.48-4.41(m,1H),3.63(d,J=4.4Hz,1H) ,2.89(dd,J=13.8,6.8Hz,1H),2.50(dd,J=13.8,8.0Hz,1H),1.19(s,9H).Car...

Embodiment 2

[0047] (S)-N-((R S )-2-(diphenylphosphino)-1-(naphthalen-2-yl)ethyl)-2-methylpropane-2-sulfinamide[1b(S,R S )]Synthesis.

[0048]

[0049] Refer to Example 1 for the specific operation, the raw material used is (R)-(+)-tert-butylsulfinamide, the nucleophile is lithium diphenylmethylenephosphine, and the total yield is 70%. Proton NMR (400MHz, CDCl 3 )δ7.79-7.75(m,3H),7.70(s,1H),7.46-7.39(m,5H),7.36-7.27(m,5H),7.21-7.18(m,3H),4.66-4.59( m,1H),3.71(d,J=4.3Hz,1H),2.98(dd,J=13.8,6.8Hz,1H),2.62(dd,J=13.8,8.0Hz,1H),1.20(s,9H ). Carbon NMR (100MHz, CDCl 3 )δ139.25(d,J C,P =4.4Hz), 138.02(d, J C,P =12.7Hz), 137.52(d, J C,P =12.9Hz), 133.13(d, J C,P =5.8Hz), 132.83(d, J C,P =3.1Hz), 132.64(d, J C,P =3.5Hz), 128.81, 128.62, 128.55, 128.32 (d, J C,P =6.7Hz), 128.02, 126.40(d, J C,P =1.1Hz), 126.11(d, J C,P =9.9Hz), 124.77, 57.73(d, J C,P =19.6Hz), 56.08, 37.16(d, J C,P =14.4Hz), 22.56; Phosphine NMR (162MHz, CDCl 3 )δ=-23.88ppm. High-resolution mass spectrometry theore...

Embodiment 3

[0051] (S)-N-((R S )-1-(diphenylphosphino)-3-methylbutan-2-yl)-2-methylpropane-2-sulfinamide[1c(S,R S )]Synthesis

[0052]

[0053] The specific operation refers to Example 1, the raw material used is (R)-(+)-tert-butylsulfinamide, the nucleophile is lithium diphenylmethylenephosphine, and the total yield is 78%. Proton NMR (400MHz, C 6 D. 6 )δ7.47-7.43(m,4H),7.16-7.03(m,6H),3.34-3.24(m,2H),2.25-2.16(m,3H),1.09(s,9H),0.87(d, J=6.8Hz, 3H), 0.72(d, J=6.9Hz, 3H). Carbon NMR (100MHz, C 6 D. 6 )δ139.79(d,J C,P =13.9Hz), 139.10(d, J C,P =15.3Hz), 133.62(d, J C,P =19.8Hz), 132.66(d, J C,P =18.3Hz), 129.08, 128.81(d, J C,P =6.9Hz), 128.74(d, J C,P =6.2Hz), 128.55, 60.41, 56.02, 33.44 (d, J C,P =6.9Hz), 32.24(d, J C,P =13.85Hz), 22.69, 18.27, 17.32; Phosphine NMR (162MHz, C 6 D. 6 )δ=-9.05ppm. High-resolution simple theoretical data C 21 h 31 NOPS:m / z(%):376.1858(M+H + ), experimental data: 376.1859.

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 provide a preparation method for a chiral tertiary phosphine compound containing chiral sulfonamide and shown as formula (1). The method takes aldehyde (ketone) 2 and chiral sulfinamide 3 as raw materials, which react with a nucleophilic reagent R2PCH2M (M=Li, K, Mgx and ZnX, etc.) to obtain the compound shown as formula (1). By using different chiral sulfinamides and different reaction reagents, the optically pure compound containing (S, Rs), (R, Rs), (S, Ss) or (R, Rs) four configurations can be prepared. The compound ligand has a simple skeleton, is convenient to synthesize and easy to transform, can be applied to various tertiary phosphine catalyzed asymmetric reactions and has very high reaction activity and stereoselectivity, thus having good application prospects. (formula 1).

Description

technical field [0001] The invention relates to a ligand or catalyst in the technical field of chemical industry and a preparation method thereof, in particular to a novel chiral phosphine compound and its full configuration, as well as its preparation method and application. Background technique [0002] Chiral drugs with a single enantiomer can be obtained through asymmetric catalysis, that is, a large number of chiral compounds can be prepared from a small amount of chiral catalysts, and the generation of invalid bodies is less or even avoided, which is not only beneficial to environmental protection, but also can achieve Good atom economy can also avoid the tedious resolution of the exobody. Designing and synthesizing chiral catalysts with high selectivity and high catalytic activity is the key to asymmetric synthesis. [0003] Chiral tertiary phosphine compounds are a very important class of chiral catalysts or ligands, which are widely used in asymmetric reactions cata...

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): C07F9/50C07F9/655C07F9/6553B01J31/24C07D307/83
Inventor 张俊良宿晓周伟李杨燕
Owner 苏州凯若利新材料科技有限公司
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