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Catalyst using phosphine-phosphoramidite ester as ligand, its preparation method and application

A phosphoramidite and catalyst technology, applied in the direction of organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problem of poor activity and enantioselectivity question

Inactive Publication Date: 2006-05-10
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Org.Lett.2002, 4(14), 2421-2424; WO 2002026750, the synthesis of Bophoz-type ferrocenephosphine-aminophosphine ligands is relatively simple, the chemical properties of the ligands are stable, and they can be stored stably in the air, but the Rh complex The compound only has good enantioselectivity (e.e=99%) for α-dehydroamino acid, and itaconic acid derivatives can only obtain higher enantioactivity under higher hydrogen pressure, but for enamide Poor or extremely poor activity and enantioselectivity of substrates such as β-dehydroamino acids and enol esters

Method used

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  • Catalyst using phosphine-phosphoramidite ester as ligand, its preparation method and application
  • Catalyst using phosphine-phosphoramidite ester as ligand, its preparation method and application
  • Catalyst using phosphine-phosphoramidite ester as ligand, its preparation method and application

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Experimental program
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Effect test

Embodiment 1

[0077] Add 7.2 grams of (R)-1-(dimethylamino)ethylferrocene and 40ml of ether to a 250ml three-necked flask, and slowly add 16.1ml of n-BuLi hexane solution with a concentration of 2.15mol / l at room temperature . After the addition was complete, the stirring reaction was continued at room temperature for 1.5 hours. The reaction mixture was warmed up to slightly boiling state, slowly added 12.4 grams of ClPPh 2 (diphenylphosphine chloride) and 20ml of diethyl ether to form a solution. After the addition was complete, the reaction was continued to reflux and stirred for 4 hours. Cool the reaction night to 0 °C, slowly add 40 ml saturated NaHCO 3(Sodium bicarbonate) aqueous solution, the addition was completed, and the stirring reaction was continued for 10 minutes. Separation, the aqueous layer was extracted twice with 50ml ether, combined ether layer, washed with 50ml water, anhydrous Na 2 SO 4 dry. Filtrate, remove the solvent under reduced pressure, and recrystallize t...

Embodiment 2

[0082] Dissolve 10.0g of (S)-1-(dimethylamino)ethylferrocene in 60ml of anhydrous ether, add 21.8ml of n-BuLi hexane solution with a concentration of 2.05mol / l at room temperature, and add for about 30 minutes. Finish. After continuing to stir and react at room temperature for 1 hour, the temperature was raised to reflux, and a solution formed by adding 6.4 g of trimethylchlorosilane and 25 ml of ether was added within 1.5 hours. The reaction solution was cooled to 5°C, and 50ml of water was added. Separate the organic phase and wash with 8.5% HO 3 PO 4 Aqueous extraction. Combine the aqueous phases with 10% Na 2 CO 3 Aqueous solution neutralized to slightly alkaline, CHCl 3 Extraction, anhydrous Na 2 SO 4 dry. The solvent was removed under reduced pressure, and the residue was purified by column chromatography (silica gel, triethylamine pretreatment, petroleum ether / ethyl acetate / triethylamine: 30 / 1 / 0.5). The solvent was removed to obtain 7.8 g of (S, R)-2[(S)-N,N-d...

Embodiment 3

[0089] Under nitrogen protection, 2.0mg (0.005mmol) [Rh(COD) 2 ] BF 4 (bicyclooctadiene rhodium complex tetrafluoroborate), the above preparation (R, S, R)-DicpPhos (0.011mmol) and solvent dichloromethane (1.5ml) are placed in a 10ml reactor, reacted for 30 After 1 min, the substrate methyl 2-acetamidoacrylate (0.5 mmol) was added with 1.5 ml CH 2 Cl 2 The formed solution was replaced with hydrogen for 3 times, and the reaction was terminated after maintaining normal pressure for 30 minutes, filtered with a short silica gel column, and after the filtered filtrate was concentrated, the content and optical purity were determined by GC to obtain S-acetylaminopropionic acid formazan The ester yield is 100% (calculated as 2-acetamidomethyl acrylate), and the enantiomeric excess is above 99% ee.

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Abstract

The invention relates to a catalyst which uses the phosphor-phosphamide as ligand, which is the phosphor-phosphamide ligand metallic complex of chiral ferrocenyl bone, wherein, the metal is rhodium, ruthenium, iridium, platinum or palladium; and the mol rate between the ligand and the metal precursor is 1.1:1-2.2:1. The ligand is compounded from chiral ferrocenyl to intermediate compound via several reaction steps, to be processed condensation with phosphite ester chloridate to attain the phosphor-phosphamide ligand with different chiral centers. Said ligand has new structure, stable property, simple compounding method, and wider application to the catalyst, which has higher catalysis activity (TON reaches 10000) and higher spatial selectivity (ee reaches more than 99%) in catalyzing asymmetry hydrogenization of itaconic acid, etc.

Description

technical field [0001] The invention relates to a catalyst, in particular to a catalyst formed from a chiral ferrocene skeleton-based phosphine-phosphoramidite ligand and a metal compound. [0002] The present invention also relates to a method for preparing the above-mentioned catalyst. [0003] The present invention also relates to the use of the above-mentioned catalysts in asymmetric hydrogenation reactions. Background technique [0004] Catalytic asymmetric hydrogenation is the core technology in asymmetric synthesis and one of the most effective methods for synthesizing optically pure chiral drugs, pesticides, food additives and spices, and the design and synthesis of chiral ligands is the key to realize this core technology factor. In ligand design, the most important principle is symmetry design. Most of the chiral bidentate phosphine ligands currently developed have C 2 - A symmetrical structure or two nearly equivalent phosphorus coordinating atoms. The existen...

Claims

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Application Information

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IPC IPC(8): B01J31/16
Inventor 郑卓胡向平
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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