Chiral monodentate phosphite ligands, its preparation method and uses

The technology of monodentate phosphite and chlorophosphite is applied in the preparation field of the above-mentioned chiral monodentate phosphite ligand, and achieves the effects of stable properties, simple process route, and stable air and humidity

Inactive Publication Date: 2007-04-25
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But so far, there is no report on the application of a class of polyethylene glycol-su

Method used

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  • Chiral monodentate phosphite ligands, its preparation method and uses
  • Chiral monodentate phosphite ligands, its preparation method and uses
  • Chiral monodentate phosphite ligands, its preparation method and uses

Examples

Experimental program
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Example Embodiment

[0076] Example 1

[0077] 1) Synthesis of monodentate phosphite ligand loaded with chiral polyethylene glycol

[0078] Add 10 grams of (R)-BINOL and 75 grams of PCl to a 100ml three-necked bottle 3 And a catalytic amount of 2-methylpyrrolidone, the reaction refluxed until the solid disappeared (about 10 minutes). Decompression removes most of the PCl 3 , A small amount of residual PCl 3 Azeotropically remove under reduced pressure with toluene. After removing the toluene, the residue was recrystallized with n-hexane to obtain 11.9 g of white chlorophosphite.

[0079] Add 3.51g of chlorophosphite and 30ml of anhydrous dichloromethane to a 100ml three-necked flask, slowly add 11g of polyethylene glycol monomethyl ether with a molecular weight of 1100 and 3.03g of triethylamine at 0°C. In 20ml of dichloromethane. After the addition, the reaction solution was raised to room temperature to continue stirring and reacting overnight. After filtration, 50 ml of ether was added to the filtr...

Example Embodiment

[0083] Example 2

[0084] Under the protection of nitrogen, 2.0mg (0.005mmol) [Rh(COD) 2 ]BF 4 , The chiral polyethylene glycol-supported monodentate phosphite ligand (0.011mmol) and solvent dichloromethane (1.5ml) prepared above were placed in a 10ml reactor. After 30 minutes of reaction, substrate 2 was added. -Methyl acetylaminocinnamate (0.5mmol) and 1.5ml CH 2 Cl 2 The resulting solution was replaced with hydrogen for 3 times, reacted for 12 hours under a hydrogen pressure of 10 atm, and then the reaction was terminated. The reaction was terminated after being filtered with a short silica gel column. After concentrating the filtrate obtained by filtration, the content and optical purity were determined by GC to obtain S-acetamido The yield of methyl phenylpropionate was 100% (calculated as methyl 2-acetamidocinnamate), and the enantiomeric excess was 92% ee or more.

Example Embodiment

[0085] Example 3

[0086] Under the protection of nitrogen, 2.0mg (0.005mmol) [Rh(COD) 2 ]BF 4 , The chiral polyethylene glycol-loaded monodentate phosphite ligand (0.011 mmol) and the solvent dichloromethane (1.5ml) prepared above were placed in a 100ml reactor, after 30 minutes of reaction, substrate 2 was added -Methyl acetamidocinnamate (50mmol) and 25ml CH 2 Cl 2 The resulting solution was replaced with hydrogen for 3 times, reacted for 12 hours under a hydrogen pressure of 10 atm, and then the reaction was terminated. The reaction was terminated after being filtered with a short silica gel column. After concentrating the filtrate obtained by filtration, the content and optical purity were determined by GC to obtain S-acetamido The yield of methyl phenylpropionate is 100% (calculated as methyl 2-acetylaminocinnamate), and the enantiomeric excess is more than 90%ee.

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Abstract

The invention discloses a chiral monodentate phosphite ester ligand and preparing method, which comprises the following steps: a) placing chiral glycol and phsophorus trichloride in the reacting bottle; adding 2-methyl pyrrolidone; heating and refluxing until the chiral glycol is dissolved completely; decompressing to remove solvent; recrystallizing residual skellysolve B; obtaining the needed phosphorochloridous acid ester; b) dissolving phosphorochloridous acid ester in the dichloromethane; adding carbowax methyl ether or carbowax methyl ester and trimethylamine carrene solution at 0-5 deg.c; heating reacting liquid to 18-25 deg.c; stirring to react 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 chiral monodentate phosphite ligand, in particular to a chiral monodentate phosphite ligand supported by polyethylene glycol. [0002] The present invention also relates to the preparation method of the above-mentioned chiral monodentate phosphite ligand. [0003] The present invention also relates to the application of the above-mentioned chiral monodentate phosphite 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 it is one of the most effective methods for the synthesis of optically pure chiral drugs, pesticides, food additives and fragrances. Among them, the synthesis of chiral ligands and the selection of central metals are the key factors to realize this core technology. The chiral ligands used in asymmetric catalytic hydrogenation are mostly unstable trivalent ph...

Claims

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Application Information

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IPC IPC(8): C07F9/6574B01J31/22C07B31/00C07C67/303
Inventor 胡向平郑卓
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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