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

Metal complex catalyst of chiral spirocyclo mono-phosphorus (phosphine) ligand and nickel, its prepn. method and application

A metal complex and catalyst technology, which is applied in the field of new nickel metal complex catalysts, can solve the problems of poor reaction results and achieve good chemoselective effects

Inactive Publication Date: 2006-06-28
NANKAI UNIV
View PDF0 Cites 3 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, most of the successful examples of ene hydrogenation are the heterodimerization of aryl ethylene and ethylene, and only a little preliminary exploration has been carried out for the ene hydrogenation of aryl polysubstituted ethylene, and the reaction results of the existing catalyst systems are relatively poor (Fassina , V.; Ramminger, C.; Seferin, M.; Monteiro, A.L. Tetrahedron 2000, 56, 7403-7409. Rajan Babu, T.V.; Nomura, N.; Jin, J.; Nandi, M.; Park, H.; Sun, X. J. Org. Chem. 2003, 68, 8431-8446)

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
  • Metal complex catalyst of chiral spirocyclo mono-phosphorus (phosphine) ligand and nickel, its prepn. method and application
  • Metal complex catalyst of chiral spirocyclo mono-phosphorus (phosphine) ligand and nickel, its prepn. method and application
  • Metal complex catalyst of chiral spirocyclo mono-phosphorus (phosphine) ligand and nickel, its prepn. method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: (S, R, R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-N,N-di-2-phenylethylphosphoramidene Preparation of Propyl Nickel Bromide Complex

[0026]

[0027] Under nitrogen atmosphere, the Ni(COD) 2 (137.5mg, 0.5mmol) was added 1mL COD (COD=1,5 cyclooctadiene), stirred for a few minutes, then allyl bromide (63.5mg, 0.525mmol) was added dropwise at 20°C, and stirred for 5~ After 10 minutes, dark blood red allyl nickel bromide dimer was obtained. Add 2 mL of toluene to it for dilution, and then add (S, R, R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-N,N-di-2-phenylethyl A solution of phosphoamidite (252 mg, 0.5 mmol) in 4 mL of toluene was stirred at 20° C. for 2 hours. The resulting orange-red mixture was filtered through celite under nitrogen atmosphere, and the filtrate was vacuum-dried to dry the solvent. The obtained red solid was vacuum-dried for 10 hours to obtain 332 mg of orange-red solid powder with a yield of 97%.

Embodiment 2

[0028] Example 2: (R, R, R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-N,N-di-2-phenylethylphosphoramidene Preparation of Propyl Nickel Bromide Complex

[0029]

[0030] Under nitrogen atmosphere, the Ni(COD) 2 (137.5mg, 0.5mmol) was added 1mL COD (COD=1,5 cyclooctadiene), stirred for a few minutes, then allyl bromide (63.5mg, 0.525mmol) was added dropwise at 20°C, and stirred for 5~ After 10 minutes, dark blood red allyl nickel bromide dimer was obtained. Add 2 mL of toluene to it for dilution, then add (R, R, R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-N,N-di-2-phenylethyl A solution of phosphoamidite (252 mg, 0.5 mmol) in 4 mL of toluene was stirred at 20° C. for 2 hours. The resulting orange-red mixture was filtered through celite under nitrogen atmosphere, and the filtrate was vacuum-dried to dry the solvent. The obtained red solid was vacuum-dried for 10 hours to obtain 335 mg of orange-red solid powder with a yield of 98%.

Embodiment 3

[0031] Example 3: Complexation of (R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-N,N-dimethylphosphoramidite allyl nickel bromide preparation

[0032]

[0033] Under nitrogen atmosphere, the Ni(COD) 2 (137.5mg, 0.5mmol) was added 1mL COD (COD=1,5 cyclooctadiene), stirred for a few minutes, then allyl bromide (63.5mg, 0.525mmol) was added dropwise at 20°C, and stirred for 5~ After 10 minutes, dark blood red allyl nickel bromide dimer was obtained. Add 2 mL of toluene to it for dilution, and then add (R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-N,N-dimethylphosphoramidite (163 mg, 0.5 mmol) in 4 mL of toluene, and continued to stir at 20°C for 2 hours. The resulting orange-red mixture was filtered through celite under nitrogen atmosphere, and the filtrate was vacuum-dried to dry the solvent. The obtained red solid was vacuum-dried for 10 hours to obtain 247 mg of yellow-green solid powder with a yield of 97%.

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

A metal complex as catalyst with wide range of application is prepared from chiral spirocyclic mono-phosphorus (mono-phosphine) ligand and Ni. It can be used in asymmetrical olefinic hydrogenation reaction to obtain a compound with chiral center. Its preparing process is also disclosed.

Description

technical field [0001] The present invention relates to a class of novel nickel metal complex catalysts, and specifically discloses a class of novel metal complexes formed with chiral spirocyclic monophosphorus (phosphine) ligands and nickel and a preparation method thereof, as well as such metal complexes. Application of the complex in the catalytic hydrogenation of asymmetric alkenes. Background technique [0002] Asymmetric catalytic synthesis is a hotspot in the field of organic synthetic chemistry research (Ohkuma, T.; Kitamura, M.; Noyori, R. Catalytic Asymmetric Synthesis, Wiley, New York, 2000). The key to asymmetric catalytic synthesis is how to design and synthesize catalysts with high enantioselectivity and high catalytic activity. The catalyst systems that have been developed with great success have greatly promoted the industrial application of asymmetric catalytic reactions and created huge economic benefits. For example, in 1975, Knowles successfully used th...

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): B01J31/22
Inventor 周其林张齐史文健朱守非王立新
Owner NANKAI 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