Phosphamide-(di) secondary amine dual-functional catalyst and synthesis method thereof

A technology of bifunctional catalysts and synthesis methods, applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc. , chiral bifunctional catalyst application reports and other issues, to achieve the effect of simple and convenient operation, stable properties, and new structure

Active Publication Date: 2015-06-10
EAST CHINA NORMAL UNIVERSITY
View PDF4 Cites 6 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Although phosphoramide catalysts have the advantages described above, in the literature survey, it was found that phosphoramide chiral catalysts are rarely used in asymmetric catalytic reactions
In particular, there are fewer reports on the application of combined phosphoramides as chiral bifunctional catalysts in the catalysis of small organic molecules.
In 2011, a class of cinchona base-derived tertiary amine-phosphoramide bifunctional catalysts (M.Ding, F.Zhou, Y.-L.Liu, C.-H.Wang, X.-L.Zhao, J.Zhou , Chem.Sci.2011,2,2035.), and applied it to the research on the asymmetric Michael addition reaction of 3-substituted oxindole and nitroalkene; although the tertiary amine-phosphoramide derived from cinchona base It has been reported, but there is almost no report on the bifunc

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
  • Phosphamide-(di) secondary amine dual-functional catalyst and synthesis method thereof
  • Phosphamide-(di) secondary amine dual-functional catalyst and synthesis method thereof
  • Phosphamide-(di) secondary amine dual-functional catalyst and synthesis method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040]

[0041] Under nitrogen protection, add cinchonidine-derived primary amine Ia (1.0 equiv) and anhydrous CH to a 50 mL round bottom flask 2 Cl 2 , after complete dissolution, triethylamine (2.0 equiv) was added. Diethoxyphosphoryl chloride IIa (1.2 equiv) was added dropwise at 0°C, stirred overnight and post-treated: add 30mL of water, extract with dichloromethane, dry over anhydrous sodium sulfate and column chromatography to obtain a white solid product IIIa, 80% yield. 1 H NMR (400MHz, CDCl 3 ):δ4.10-4.04(m,4H),2.63-2.56(m,2H),2.29-2.28(m,1H),2.05-2.02(m,1H),1.94-1.91(m,1H),1.67 (s,br,2H),1.59(s,2H),1.31(t,J=6.8Hz,6H),1.25-1.05(m,4H); 13 C NMR (100MHz, CDCl 3 ):δ62.46,62.42,58.89,56.66(d,J C-P =6.5Hz,1C),34.85,34.67,25.37,24.92,16.26,16.19; 31 P NMR (161.7MHz, CDCl 3 ):δ9.03(s,1P).MS(EI):250(M + ,0.4),154(25),126(13),97(100),96(22),44(39);HRMS(EI):Exact mass calcd for C 10 h 23 N 2 o 3 P[M] + :250.1446,Found:250.1445.

Embodiment 2

[0043]

[0044] Under nitrogen protection, add cinchonidine-derived primary amine Ia (1.0 equiv) and anhydrous CH to a 50 mL round bottom flask 2 Cl 2 , after complete dissolution, triethylamine (2.0 equiv) was added. Diethoxyphosphoryl chloride IIa (1.0 equiv) was added dropwise at 0°C, stirred overnight and post-treated: add 30mL of water, extract with dichloromethane, dry over anhydrous sodium sulfate and perform column chromatography to obtain a white solid product IIIa, 80% yield. Then, under nitrogen protection, add anhydrous EtOH after adding IIIa in the Schlenk bottle, add 1-naphthaldehyde (1.2equiv) at room temperature, after the reaction system was stirred for 1 hour under reflux conditions (TLC detects that the reaction is complete), the The reaction system was transferred to an ice-water bath for cooling, then sodium borohydride (2.0 equivs) was slowly added, stirred in an ice-water bath for about 2 hours, and the reaction was complete, and NaHCO was added 3 ...

Embodiment 3

[0046]

[0047] Under nitrogen protection, add cinchonidine-derived primary amine Ia (1.0 equiv) and anhydrous CH to a 50 mL round bottom flask 2 Cl 2 , after complete dissolution, triethylamine (2.0 equiv) was added. Add diisopropoxyphosphoryl chloride IIb (1.0 equiv) dropwise at 0°C, stir overnight, and then perform post-treatment: add 30 mL of water, extract with dichloromethane, dry over anhydrous sodium sulfate, and column chromatography to obtain a white solid Product IIIb, yield 57%. Then under nitrogen protection, add anhydrous EtOH after adding IIIb in the Schlenk bottle, add 1-naphthaldehyde (1.2equiv) at room temperature, and the reaction system is stirred under reflux conditions after 1 hour (TLC detects that the reaction is complete), and The reaction system was transferred to an ice-water bath for cooling, then sodium borohydride (2.0 equivs) was slowly added, stirred in an ice-water bath for about 2 hours, and the reaction was complete, and NaHCO was added ...

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 phosphamide-(di) secondary amine dual-functional catalyst and a synthesis method thereof. The structure of the catalyst is represented as follows, and the synthesis method comprises the steps of performing reaction on simple and readily available chiral 1,2-diamine and various phosphoryl chloride, and performing reaction with an aldehyde compound to prepare the phosphamide-(di) secondary amine dual-functional catalyst with chirality and efficient catalysis activity. The prepared catalyst is novel in structure and stable in property; the synthesis method is simple, and the catalysis activity is high; the synthesis method is simple and has the outstanding characteristics of wide application range, mild reaction condition, simplicity and convenience in operation and the like. The structural formula of the catalyst is shown in the description.

Description

technical field [0001] The invention belongs to the technical field of organic compounds, and relates to a novel phosphoramide-(primary) secondary amine bifunctional catalyst and a synthesis method thereof. Background technique [0002] Bifunctional catalysts refer to compounds containing two functional groups in the same catalyst molecule. Since there are two functional groups in the molecule at the same time, it is possible for one functional group to deactivate the electrophile and the other to deactivate the nucleophile in the reaction, which not only shortens the spatial distance between the two reaction substrates, making the reaction similar to Occurs within the molecule, and at the same time due to the dual activation, the reaction substrate is better activated, thereby improving the activity and selectivity of the reaction. [0003] Hydrogen bond donor bifunctional catalyst means that one functional group in the catalyst molecule is a hydrogen bond donor functional...

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): B01J31/02C07F9/24C07D209/34
Inventor 周剑余金生
Owner EAST CHINA NORMAL UNIVERSITY
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
Try Eureka
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap