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Phosphine-phosphoramidite ligand, its preparation method and uses

A phosphoramidite and ligand technology, which is applied in the preparation field of the above-mentioned ligands, and achieves the effects of stable catalyst properties and wide application range of pressure

Active Publication Date: 2007-04-25
DALIAN TRICO CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But so far, apart from the reported DICPPhos, only QUNIPHOS has achieved better enantioselectivity in the asymmetric catalytic reaction of methyl α-acetamidoacrylate and dimethyl itafuate

Method used

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  • Phosphine-phosphoramidite ligand, its preparation method and uses
  • Phosphine-phosphoramidite ligand, its preparation method and uses
  • Phosphine-phosphoramidite ligand, its preparation method and uses

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0076] 1) Ligand synthesis

[0077] Add 1.16 g of (S)-1-phenylethylamine and 10 ml of ether into a 100 ml three-necked flask, and slowly add 5.98 ml of n-BuLi hexane solution with a concentration of 1.6 mol / l at room temperature. After the addition was complete, the stirring reaction was continued at 0° C. for 15 minutes, and then 1.33 ml of trimethylchlorosilane was added. After reacting for 1 hour, 17.9 ml of n-BuLi hexane solution with a concentration of 1.6 mol / l was added slowly, and the reaction mixture was slowly raised from room temperature to room temperature within 5 hours. After reacting for 1 hour, the reaction night was cooled to -20°C, and a solution formed of 1.72ml of diphenylphosphine chloride and 10ml of diethyl ether was added slowly. Warm to room temperature and stir the reaction overnight. Add 40ml saturated NaHCO 3 After the addition of the aqueous solution was completed, the stirring reaction was continued for 10 minutes. Separation, the aqueous laye...

Embodiment 2

[0083] Under nitrogen protection, 2.0mg (0.005mmol) [Rh(COD) 2 ] BF 4 , the above-mentioned prepared chiral phosphine-phosphoramidite ligand (0.011mmol) and solvent dichloromethane (1.5ml) were placed in a 10ml reactor, and after 30 minutes of reaction, the substrate 2-acetamidocinnamic acid was added Methyl ester (0.5mmol) with 1.5ml CH 2 Cl 2 The formed solution was replaced with hydrogen for 3 times, reacted for 12 hours under a hydrogen pressure of 10 atm, filtered through a short silica gel column, concentrated the filtered filtrate, and measured its content and optical purity with GC to obtain S-acetamidobenzenepropane The yield of methyl acid is 100% (calculated as methyl 2-acetamidocinnamate), and the enantiomeric excess is above 90% ee.

Embodiment 3

[0085]Under nitrogen protection, 2.0mg (0.005mmol) [Rh(COD) 2 ] BF 4 , the above-mentioned prepared chiral phosphine-phosphoramidite ligand (0.011mmol) and solvent methylene chloride (1.5ml) were placed in a 100ml reactor, after reacting for 30 minutes, the substrate 2-acetylaminocinnamic acid was added Methyl ester (50mmol) and 25ml CH 2 Cl 2 The formed solution was replaced with hydrogen for 3 times, reacted for 12 hours under a hydrogen pressure of 10 atm, filtered through a short silica gel column, concentrated the filtered filtrate, and measured its content and optical purity with GC to obtain S-acetamidobenzenepropane The yield of methyl acid is 100% (calculated as methyl 2-acetamidocinnamate), and the enantiomeric excess is above 90% ee.

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Abstract

The invention discloses a chiral phosphor-phosphorous amide ester ligand and preparing method, which is characterized by the following: dissolving phosphorochloridous acid ester in the toluene; setting the molar rate of chiral phosphor-amino, phosphorochloridous acid ester and trimethylamine at 1:1-2:3-5; adding chiral phosphor-amino and trimethylamine in the toluene to form solution; heating the solution to 18-25 deg.c; stirring for 10-30h; filtering; removing solvent to obtain the product. The invention improves catalyzing activity, which makes TON at 10000.

Description

technical field [0001] The invention relates to a phosphine-phosphoramidite ligand based on a chiral phenethylamine skeleton. [0002] The present invention also relates to the preparation method of the above-mentioned ligand. [0003] The present invention also relates to the application of the above-mentioned ligand in the asymmetric hydrogenation reaction of C=C, C=O, C=N and other double bonds. 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 existence of this sym...

Claims

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Application Information

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IPC IPC(8): C07F9/6564C07F9/6571
Inventor 胡向平郑卓
Owner DALIAN TRICO CHEM