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Method for synthesizing chiral ferrocene diphosphine ligand

A technology of chiral ferrocene and synthesis method, which is applied in the field of synthesis of chiral ferrocene bisphosphine ligands, can solve problems such as inconvenient operation, and achieve the effects of simplified operation, high quality, and meeting the requirements of industrial production

Inactive Publication Date: 2009-11-04
WUHAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In the method reported in the literature (Bull.Chem.Soc.Jpn., 53,1138-1151), ferrocene is used as a raw material through multi-step synthesis, and multiple chromatographic separations and purifications are used in the route, which is inconvenient to operate

Method used

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  • Method for synthesizing chiral ferrocene diphosphine ligand
  • Method for synthesizing chiral ferrocene diphosphine ligand
  • Method for synthesizing chiral ferrocene diphosphine ligand

Examples

Experimental program
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Effect test

Embodiment 1

[0059] The synthesis method of bisphosphine ligand is achieved through the following steps:

[0060] A) Synthesis of acetylferrocene(II)

[0061] Add 18.6g ferrocene (I), 14g aluminum trichloride, and 60ml petroleum ether into a 250ml three-necked flask with mechanical stirring, reflux and dropping funnel, and slowly add 11ml of acetyl chloride in about 30 minutes. Finish dripping. After reacting at 50°C for 4 hours, the reaction solution was poured into water, the organic layer was separated, the aqueous layer was extracted with the organic solvent dichloromethane, the organic layers were combined, dried, and concentrated to obtain about 21 g of pure acetylferrocene (II). The rate is 92%. Melting point 83-85°C.

[0062] 1 H NMR(CDCl 3 ): δ4.77 (s, 2H), 4.50 (s, 2H), 4.21 (s, 4H), 2.40 (s, 3H); 13 C NMR (CDCl): δ 201.9, 79.0, 72.2, 69.7, 69.4, 27.2.

[0063] 2) Preparation of ferrocene ethanol (III)

[0064] Add 22.8g of acetylferrocene (II), 38ml of methanol, and 5.4g of potassiu...

Embodiment 2

[0086] The synthesis method of bisphosphine ligand is achieved through the following steps:

[0087] A) Synthesis of acetylferrocene (II)

[0088] 18.6g ferrocene (I), 12g alumina, 60ml dichloromethane were added to a 250ml three-necked flask connected with mechanical stirring, reflux and dropping funnel, and 21ml acetyl chloride was added dropwise within 30 minutes. After reacting at 60°C for 5 hours, the reaction solution was poured into 100ml of water, the organic layer was separated, the aqueous layer was extracted with organic solvent dichloromethane, the organic layers were combined, dried and concentrated to obtain about 21.9g pure acetylferrocene(II) , The yield is 96%. Melting point 83-85°C.

[0089] 1 H NMR(CDCl 3 ): δ4.77 (s, 2H), 4.50 (s, 2H), 4.21 (s, 4H), 2.40 (s, 3H); 13 C NMR (CDCl): δ 201.9, 79.0, 72.2, 69.7, 69.4, 27.2.

[0090] 2) Preparation of ferrocene ethanol (III)

[0091] Add 21.9g of acetylferrocene (II), 38ml of methanol, 2.3g of sodium to a 250ml single...

Embodiment 3

[0113] The synthesis method of bisphosphine ligand is achieved through the following steps:

[0114] A) Synthesis of acetylferrocene (II)

[0115] 18.6g ferrocene (I), 13.6g zinc chloride, and 60ml toluene were added to a 250ml three-necked flask with mechanical stirring, reflux and dropping funnel, and 21ml acetyl chloride was slowly added dropwise within 30 minutes. After reacting at 60°C for 5 hours, the reaction solution was poured into 100 ml of water, the organic layer was separated, the aqueous layer was extracted with the organic solvent dichloromethane, the organic layers were combined, dried, and concentrated to obtain about 22 g of pure acetylferrocene (II). The yield was 96.5%. Melting point 83-85°C.

[0116] 1 H NMR(CDCl 3 ): δ4.77 (s, 2H), 4.50 (s, 2H), 4.21 (s, 4H), 2.40 (s, 3H); 13 C NMR (CDCl): δ 201.9, 79.0, 72.2, 69.7, 69.4, 27.2.

[0117] 2) Preparation of ferrocene ethanol (III)

[0118] Add 2.28 g of acetylferrocene (II), 4 ml of tetrahydrofuran, and 10 ml of...

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Abstract

The invention relates to a method for synthesizing chiral ferrocene diphosphine ligand. The method comprises the following steps: ferrocene as a raw material is prepared into acetylferrocene through a Friedel-Crafts reaction; the acetylferrocene is prepared into N,N-dimethylamine ethyl ferrocene through reduction, esterification and amination; and the N,N-dimethylamine ethyl ferrocene is resolved by chiral acid to obtain chiral acid salt of R-N,N-dimethylamine ethyl ferrocene; the chiral acid salt of the R-N,N-dimethylamine ethyl ferrocene is analyzed to obtain optical pure R-N,N-dimethylamine ethyl ferrocene; the obtained R-N,N-dimethylamine ethyl ferrocene reacts with organic lithium base; dialkyl phosphonium chloride is added to the reactant to obtain 1-S-dialkyl phosphonium-2-R-N,N-dimethylamine ethyl ferrocene; and 1-S-dialkyl phosphonium-2-R-N,N-dimethylamine ethyl ferrocene further reacts with another dialkyl phosphonium to obtain chiral diphosphine ligand 1-S-dialkyl phosphino-2-R-dialkyl phosphino ferrocene. The method simplifies operation, has low production cost, and can be used for industrial production.

Description

Technical field [0001] The invention relates to a method for synthesizing a chiral ferrocene bisphosphine ligand, which belongs to the technical field of organic chemistry and also to the technical field of medicinal chemistry. Background technique [0002] The chiral ferrocene bisphosphine ligand is an important ligand in the preparation of asymmetric catalytic hydrogenation catalysts. It has been widely used in asymmetric hydrogenation and is a model of asymmetric catalytic reaction in industrial applications. Since the 1970s, It has always been the focus and research focus of the domestic and foreign pharmaceutical industry. In asymmetric catalysis, the commonly used catalyst ligands are bisphosphine ligands. Most bisphosphine ligands are easily oxidized, while the ferrocene-based bisphosphine ligands are relatively stable and have been widely used in large-scale asymmetric catalysis. Hydrogenation reaction. [0003] The method reported in the literature (Bull. Chem. Soc. Jpn....

Claims

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Application Information

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IPC IPC(8): C07F17/02C07B57/00B01J31/24
CPCC07F17/02
Inventor 申永存徐维赟李学超
Owner WUHAN UNIV OF TECH
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