1,2-disubstituted bis ruthenium face chirality ligand and method for synthesizing same

A technology of ruthenocene faces and chiral ligands, which is applied in 1 field and can solve problems such as low ligand reactivity and poor asymmetry induction effect

Inactive Publication Date: 2008-03-12
SHANGHAI JIAO TONG UNIV +1
View PDF0 Cites 3 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage is that the reactivity of the ligand is

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
  • 1,2-disubstituted bis ruthenium face chirality ligand and method for synthesizing same
  • 1,2-disubstituted bis ruthenium face chirality ligand and method for synthesizing same

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] 1, the preparation of 1-dicarboxyruthenocene (1)

[0032] Add ruthenocene (0.23g, 1mmol), m-chlorobenzoyl chloride (0.18g, 1mol) and dichloromethane (5mL) into a 250mL two-necked flask. Cool down to 0-2°C, add anhydrous aluminum trichloride (0.14 g, 1 mmol) in batches, wait for the temperature to rise naturally and stir overnight. Cool down to 0-2°C, add water (2mL) carefully, stir for 2h, then dilute the system with dichloromethane (20mL), wash with 10% sodium hydroxide solution, water and saturated brine successively, and anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was subjected to column chromatography (ethyl acetate / petroleum ether=1 / 20) to obtain an acylated product (51.5 mg, y=13.9%).

[0033] 1 H NMR (400MHz, CDCl 3 ): δ4.64(s, 5H), 4.83(tJ=2Hz, 2H), 5.01(tJ=2Hz, 2H), 7.28-7.55(m, 4H), 7.99-8.05(m, 1H).

[0034] 2-Chlorobenzoylruthenocene (8.2g, 22mmol) and potassium tert-butoxide (9.9g, 88mmol) were adde...

Embodiment 2

[0044] 1, the preparation of 1-dicarboxyruthenocene (1)

[0045] Into a 250 mL two-necked flask were added ruthenocene (0.23 g, 1 mmol), m-chlorobenzoyl chloride (2.7 g, 15 mol) and dichloromethane (5 mL). Cool down to 0-2°C, add anhydrous aluminum trichloride (0.42g, 3mmol) in batches, wait for the temperature to rise naturally and stir overnight. Cool down to 0-2°C, add water (2mL) carefully, stir for 2h, then dilute the system with dichloromethane (20mL), wash with 10% sodium hydroxide solution, water and saturated brine successively, and anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was subjected to column chromatography (ethyl acetate / petroleum ether=1 / 20) to obtain an acylated product (168 mg, y=65.4%).

[0046] 1 H NMR (400MHz, CDCl 3 ): δ4.64(s, 5H), 4.83(t J=2 Hz, 2H), 5.01(t J=2 Hz, 2H), 7.28-7.55(m, 4H), 7.99-8.05(m, 1H) .

[0047] 2-Chlorobenzoylruthenocene (8.2g, 22mmol) and potassium tert-butoxide (9.9g, 8...

Embodiment 3

[0057] 1, the preparation of 1-dicarboxyruthenocene (1)

[0058] Add ruthenocene (11.6 g, 50 mmol), m-chlorobenzoyl chloride (63 mL, 0.5 mol) and dichloromethane (100 mL) into a 250 mL two-necked flask. Cool down to 0-2°C, add anhydrous aluminum trichloride (8.7 g, 65 mmol) in batches, wait for the temperature to rise naturally and stir overnight. Cool down to 0-2°C, add water (20mL) carefully, stir for 2h, then dilute the system with toluene (200mL), wash with 10% sodium hydroxide solution, water and saturated brine successively, anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure. The residue was subjected to column chromatography (ethyl acetate / petroleum ether=1 / 20) to obtain an acylated product (13.5 g, y=73%).

[0059] 1 H NMR (400MHz, CDCl 3 ): δ4.64(s, 5H), 4.83(tJ=2Hz, 2H), 5.01(tJ=2Hz, 2H), 7.28-7.55(m, 4H), 7.99-8.05(m, 1H).

[0060]2-Chlorobenzoylruthenocene (8.2g, 22mmol) and potassium tert-butoxide (9.9g, 88mmol) were added to...

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 present invention relates to 1, 2- substitute cyclopentadienyl ruthenium surface chiral ligand in the chemical field and the correspondence synthetic method. The present invention comprises six reaction steps: the cyclopentadienyl ruthenium, after the Fuke acyl reaction, is hydrolyzed into 1-carboxyl cyclopentadienyl ruthenium; then 1-carboxyl cyclopentadienyl ruthenium reacts with oxalyl chloride to generate 1-carboxyl carbonyl cyclopentadienyl ruthenium; 1-oxazoline carboxyl carbonyl cyclopentadienyl ruthenium reacts with beta-amino alcohol to generate lactam compound, and then reacts with methane-sulfonyl chloride to generate 1-oxazoline cyclopentadienyl ruthenium; 1-oxazoline cyclopentadienyl ruthenium reacts with sec-butyllithium first, and then reacts with diphenyl chloride phosphate to generate (S, Sp)-1,2-substitute cyclopentadienyl ruthenium P, N- ligand; 1-oxazoline cyclopentadienyl ruthenium reacts with sec-butyllithium first, and then reacts with trimethylchlorosilane to generate (S,Sp)-1- oxazoline-2-trimethyl cyclopentadienyl ruthenium. Then the trimethyl is shucked off to generate (S,Rp)-1,2-substitute cyclopentadienyl ruthenium P,N- ligand. The structure is as follows: in the formula: R: a represents isopropyl, b represents tert-butyl.

Description

technical field [0001] The invention relates to a chiral ligand in the technical field of chemical engineering and a synthesis method thereof, in particular to a 1,2-disubstituted ruthenocene chiral ligand used in asymmetric catalytic reactions and a synthesis method thereof. technical background [0002] The rapid rise of the chiral drug industry is mainly due to the great development of asymmetric synthesis methodology research, and in turn, the chiral drug industry has promoted the research of asymmetric synthesis methodology. Asymmetric catalytic organic synthesis is one of the most effective and beneficial methods to obtain chiral compounds. In asymmetric catalytic organic synthesis, the key to high reactivity and high enantioselectivity lies in the structure of chiral ligands. Among them, the synthesis and application of chiral phosphine nitrogen ligands have always been valued by chemists. [0003] Found through literature search to prior art, Sammakia et al publish...

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): C07F17/02
CPCC07B2200/07C07F17/02C07B53/00B01J31/189C07C29/145
Inventor 张万斌谢芳刘德龙
Owner SHANGHAI JIAO TONG 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