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Chiral diphosphine ligand and application thereof to asymmetric hydrogenation and correlated reactions

A technology of chiral bisphosphine ligands and chiral phosphine ligands, applied in the field of chiral bidentate phosphine ligands

Active Publication Date: 2016-04-13
WUHAN CATALYS TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, since no chiral catalyst is omnipotent in asymmetric catalytic reactions, different types of reactions often require different types of ligands. Phosphine ligands are important

Method used

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  • Chiral diphosphine ligand and application thereof to asymmetric hydrogenation and correlated reactions
  • Chiral diphosphine ligand and application thereof to asymmetric hydrogenation and correlated reactions
  • Chiral diphosphine ligand and application thereof to asymmetric hydrogenation and correlated reactions

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Experimental program
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Effect test

Embodiment 1

[0033] The preparation of embodiment 1 intermediate 1:

[0034]

[0035] (s)-2-Dimethylamino-ethylferrocene (2.5715 g) and 10 mL of anhydrous diethyl ether were sequentially added to a 100 mL Schlunk flask replaced with a nitrogen atmosphere. To the obtained solution was added dropwise 1.5M tert-butyl lithium in pentane solution (7.6 mL) at -78°C, and the reaction was carried out at room temperature for 1.5 h. After the reaction liquid was cooled to -78°C, phosphine trichloride (1 mL) was added, and the resulting reaction liquid was raised to room temperature for 1.5 h. After the reaction solution was cooled to -78°C, 2-bromo-phenylmagnesium chloride (10 mmol) prepared in advance was added, and the reaction was carried out at room temperature for 1.5 h. After cooling the reaction solution to -78°C again, 3.0M methylmagnesium chloride (3.8mL) was added, and the resulting solution was raised to room temperature and reacted for 3h, then 10mL of water was added to separate the...

Embodiment 2

[0036] The preparation of embodiment 2 ligand L1:

[0037]

[0038] Intermediate 1 (1.3746 g) and 20 mL of anhydrous diethyl ether were sequentially added into a 50 mL Schlunk flask replaced with a nitrogen atmosphere. To the obtained solution was added dropwise 2.3M n-butyllithium hexane solution (1.4 mL) at -78°C, and the mixture was raised to room temperature for 1 h. After the reaction solution was cooled to -78°C, diphenylphosphine chloride (704 mg) was added, and the resulting reaction solution was raised to room temperature for 3 hours, then 20 mL of water was added, the organic phase was separated, and the aqueous phase was extracted three times with ethyl acetate (each 20mL). The obtained organic phase was dried over anhydrous sodium sulfate and then spin-dried under reduced pressure. The crude product was purified by column chromatography to obtain the target product ligand L1 (1.40 g, yield 83%).

Embodiment 3

[0039] The preparation of embodiment 3 ligand L2:

[0040]

[0041] Intermediate 1 (1.3746 g) and 20 mL of anhydrous diethyl ether were sequentially added into a 50 mL Schlunk flask replaced with a nitrogen atmosphere. To the obtained solution was added dropwise 2.3M n-butyllithium hexane solution (1.4 mL) at -78°C, and the mixture was raised to room temperature for 1 h. After cooling the reaction solution to -78°C, dicyclohexylphosphine chloride (767.9 mg) was added, and the resulting reaction solution rose to room temperature and reacted for 3 hours, then 20 mL of water was added to separate the organic phase, and the aqueous phase was extracted three times with ethyl acetate (each times 20mL). The obtained organic phase was dried over anhydrous sodium sulfate and then spin-dried under reduced pressure. The crude product was purified by column chromatography to obtain the target product ligand L2 (1.47 g, yield 85%).

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Abstract

The invention discloses a chiral diphosphine ligand based on a ferrocene framework and application thereof to asymmetric hydrogenation and correlated reactions. The novel chiral diphosphine ligand possesses a structure shown as a general formula I. In the general formula I, R1 is methyl, phenyl, t-butyl, hydroxyl and the like, R2 is ethyl, phenyl, cyclohexyl, p-mehtylphenyl, t-butyl, 3,5-dimethylphenyl, 3,5-di-t-butylphenyl, 3,5-di-t-butyl-4-methoxyphenyl, 2,6-dimethoxyphenyl, 2,6-dimethylphenyl and anthryl, and the bridging group between two phosphorus atoms is phenyl, naphthyl, alkyl and the like. Also, the invention discloses synthesis of the novel chiral diphosphine ligand and application of the chiral diphosphine ligand to prepare chiral medicines ibuprofen, naproxen and the like.

Description

technical field [0001] The invention relates to a chiral bidentate phosphine ligand based on a ferrocene skeleton and its application in asymmetric hydrogenation and related reactions. Background technique [0002] Chiral phosphine ligands play an important role in asymmetric reactions catalyzed by transition metals. So far, hundreds of chiral phosphine ligands and corresponding patented technologies have been reported. However, since no chiral catalyst is omnipotent in asymmetric catalytic reactions, different types of reactions often require different types of ligands. Phosphine ligands are of great importance. [0003] Ferrocene-type chiral bisphosphine ligands have been extensively reported, and representative phosphine ligands are shown below. These ligands all have C-chirality and face chirality. Based on their superior chiral induction effect, these ligands show very good enantioselectivity in some asymmetric catalytic reactions. [0004] [0005] Based on the s...

Claims

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Application Information

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IPC IPC(8): C07F17/02B01J31/22C07B53/00C07C51/36C07C67/08C07C67/303C07C231/18C07C57/58C07C59/64C07C59/01C07C69/675C07C69/34C07C233/47
CPCB01J31/2295B01J2231/645B01J2531/0258B01J2531/0263B01J2531/822C07B53/00C07B2200/07C07C51/36C07C67/08C07C67/303C07C231/18C07F17/02C07C57/58C07C59/64C07C59/01C07C69/675C07C69/34C07C233/47
Inventor 张绪穆陈才友
Owner WUHAN CATALYS TECH CO LTD
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