Chiral quaternary ammonium salt phase transfer catalyst based on tetramethyl spirobiindane skeleton and preparation method thereof

A technology of tetramethylspirodihydroindene and phase transfer catalyst, applied in the field of chemistry, can solve problems such as unsatisfactory stereoselectivity, and achieve the effects of easy structure modification and simple operation

Active Publication Date: 2021-06-08
LANZHOU JIAOTONG UNIV
View PDF6 Cites 2 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Although the above catalysts have achieved great success in many reactions, the stereoselectivity of these asymmetric phase transfer catalysts reported so far for some important reactions is not ideal.

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 quaternary ammonium salt phase transfer catalyst based on tetramethyl spirobiindane skeleton and preparation method thereof
  • Chiral quaternary ammonium salt phase transfer catalyst based on tetramethyl spirobiindane skeleton and preparation method thereof
  • Chiral quaternary ammonium salt phase transfer catalyst based on tetramethyl spirobiindane skeleton and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053]

[0054] Under nitrogen protection, (R)-II (1.5g, 2.39mmol), tetrakis(triphenylphosphine) palladium (277.3mg, 0.24mmol), 3,5-diphenylbenzene Boric acid (1.64g, 5.98mmol), anhydrous potassium carbonate (1.32g, 9.56mmol), DMF (55mL), the reaction solution was heated to 70°C and stirred for 8 hours. After the reaction was complete, the reaction solution was cooled to room temperature, the reaction solution was quenched with 10 mL of distilled water, and extracted with EtOAc (150 mL), the organic phase was washed with deionized water (5×100 mL), and then washed with saturated brine (100 mL), Dry over anhydrous sodium sulfate, filter, and remove the organic solvent by rotary evaporation under reduced pressure. The obtained crude product is purified by silica gel column chromatography, and the eluent is ethyl acetate:petroleum ether=1:100-1:50 to obtain (R)-1a It is 1.72g, is a white solid, and the yield is 92%; 1 H NMR (500MHz, CDCl 3 )δ9.68(2H,s),7.76(2H,t,J=10.0Hz),7....

Embodiment 2

[0059]

[0060] Under nitrogen protection, (R)-II (1 g, 1.6 mmol), tetrakis(triphenylphosphine) palladium (277 mg, 0.24 mmol), 3,5-bis(tert-butyl) were sequentially added to a dry Schlenk tube Phenylboronic acid (1.5g, 6.4mmol), then tetrahydrofuran (50mL), methanol (2mL) and 2M potassium carbonate solution (5mL) were added; the reaction solution was stirred under reflux for 5 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and the reaction solution was concentrated in vacuo. The obtained crude product was extracted with EtOAc (3×100 mL), and the organic phase was washed with saturated brine (100 mL), dried over anhydrous sodium sulfate, filtered, and reduced pressure. The organic solvent was removed by rotary evaporation, and the obtained crude product was purified by silica gel column chromatography, the eluent was ethyl acetate:petroleum ether=1:100-1:50, and (R)-1b was obtained as 1.13g as a white solid, the yield 99%. 1 H ...

Embodiment 3

[0065] According to the reaction process similar to Example 2, the following chiral compounds can be prepared, and the structure, yield and characterization data are as follows:

[0066]

[0067] According to the reaction process similar to Example 2, the reaction time was 15 hours, the crude product was recrystallized with dichloromethane:petroleum ether=1:8, the yield was 99%, and it was a white solid; 1H NMR (500MHz, CDCl 3 )δ7.43(2H, t, J=1.8Hz),7.41(2H,d,J=8.0Hz),7.35(2H,d,J=7.8Hz),7.18(4H,br),4.81 (2H, d,J=14.0Hz),4.62(2H,d,J=14.0Hz),3.26-3.37(2H,m),2.69-2.77(2H,m), 2.58(2H,d,J=13.0Hz), 2.41-2.56(4H,m),2.37(2H,d,J=13.0Hz),1.59(6H,s), 1.56(6H,s),1.33(36H,s); 13 C NMR (125MHz, CDCl 3 )δ152.58, 152.34, 152.08, 145.78, 139.59, 131.67, 126.24, 124.80, 121.92, 117.81, 61.11, 61.08, 57.45, 57.10, 42.25, 35.21, 32.70, 31.66. M] + calcd for C 55 h 74 NO + 764.5765,found:764.5764.Mp 233-234℃.[α] D 25 =+136.0° (c=1.0, CHCl 3 ).

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 chiral quaternary ammonium salt phase transfer catalyst based on a tetramethyl spirobiindane skeleton and a preparation method thereof. The quaternary ammonium salt compound is a compound with a structure as shown in a general formula (I) or an enantiomer, a racemate or a diastereomer of the compound. The novel chiral quaternary ammonium salt compound with the spiro skeleton developed by the invention can be used for catalyzing an organic reaction, and particularly has an excellent catalytic effect in a glycine Schiff base asymmetric alkylation reaction as a chiral phase transfer catalyst.

Description

technical field [0001] The invention belongs to the field of chemistry, and specifically relates to a chiral quaternary ammonium salt phase transfer catalyst based on a tetramethylspirodihydroindene skeleton, a preparation method thereof and an application thereof in an asymmetric alkylation reaction of glycine Schiff base. Background technique [0002] Asymmetric catalytic reactions use catalytic amounts of chiral raw materials to stereoselectively produce a large number of chiral products, which is the most efficient way to obtain optically active molecules and is one of the most active research fields in chemical science today. Among them, chiral phase transfer catalysis, as one of the important branches in the field of asymmetric catalysis, has the advantages of simple operation, mild conditions, low cost, environmental friendliness and industrialization, and has been widely used in scientific research and industry. Chiral phase transfer catalysts mainly include chiral q...

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): B01J31/02C07D225/04C07B53/00C07C249/02C07C251/24
CPCB01J31/0239C07B53/00C07B2200/07C07C249/02C07D225/04C07C251/24
Inventor 徐长明齐银生
Owner LANZHOU JIAOTONG UNIV
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