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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

AI Technical Summary

Problems solved by technology

But so far, there is no report on the application of a class of polyethylene glycol-supported monodentate phosphite ligands in asymmetric catalytic hydrogenation reactions.

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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Effect test

Embodiment 1

[0077] 1) Synthesis of monodentate phosphite ligand supported by 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 was refluxed until the solid disappeared (about 10 minutes). Remove most of PCl under reduced pressure 3 , a small amount of residual PCl 3 Azeotroped removal with toluene under reduced pressure. After the toluene was removed, the residue was recrystallized from n-hexane to obtain 11.9 g of white phosphorochloride.

[0079] Add 3.51 grams of chlorophosphite and 30 ml of anhydrous dichloromethane into a 100 ml three-necked bottle, slowly add 11 grams of polyethylene glycol monomethyl ether with a molecular weight of 1100 and 3.03 grams of triethylamine to dissolve A solution formed in 20 ml of dichloromethane. After the addition was complete, the reaction solution was raised to room temperature and continued to stir overnight. After fil...

Embodiment 2

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

Embodiment 3

[0086] Under nitrogen protection, 2.0mg (0.005mmol) [Rh(COD) 2 ] BF 4 , the monodentate phosphite ligand (0.011mmol) and the solvent methylene chloride (1.5ml) prepared above were placed in a 100ml reactor, reacted for 30 minutes, and added substrate 2 - Methyl acetylaminocinnamate (50mmol) with 25ml CH 2 Cl 2 The formed solution was replaced with hydrogen for 3 times, then reacted under a hydrogen pressure of 10 atm for 12 hours, then terminated the reaction, filtered through a short silica gel column, concentrated the filtered filtrate, and determined its content and optical purity by GC to obtain S-acetylamino The yield of methyl phenylpropionate is 100% (calculated as methyl 2-acetylamino cinnamate), 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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