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Chiral ruthenium catalyst and use thereof in asymmetric hydrogenation of ketone

A technology of ruthenium catalyst and hydrogenation reaction, which is applied in the field of chiral metal ruthenium catalyst and its application in ketone asymmetric hydrogenation reaction, can solve the problems of high cost and high catalyst cost, and achieve simple structure, low cost and strong practicability Effect

Inactive Publication Date: 2011-04-06
LANZHOU 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

Based on this, a large number of chiral catalysts for asymmetric hydrogenation reactions have been developed. The most representative chiral catalyst is the BINAP[2,2′ -bis-(diphenylphosphino)-1,1'-binaphthyl] chiral metal ruthenium catalyst (its representative patents are EP0901997A1, JP2000026344A, JP2003104993A, US6720439B1, WO01 / 58843A1 and WO02 / 062809A1), but in the above-mentioned patent method The catalysts used all use expensive chiral phosphine ligands, and the cost of the catalyst is high

Method used

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  • Chiral ruthenium catalyst and use thereof in asymmetric hydrogenation of ketone
  • Chiral ruthenium catalyst and use thereof in asymmetric hydrogenation of ketone
  • Chiral ruthenium catalyst and use thereof in asymmetric hydrogenation of ketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Example 1: Preparation of (s)-1-phenylethyl alcohol 2a from acetophenone 1a

[0040]

[0041] Under an argon atmosphere, the catalyst Cat.1 (0.1%, 0.0025mmol), acetophenone 1a (300mg, 2.5mmol) and KO t Bu (28 mg, 0.25 mmol) was dissolved in n-PrOH (2.5 ml) and placed in an autoclave. Fill the autoclave with 10 atm hydrogen and stir at room temperature for 10 h. After the reaction, the solvent was drained and separated by column chromatography (using a silica gel column; eluent: petroleum ether / ethyl acetate=5 / 1) to obtain pure product 2a. The product was a colorless liquid (98% ee, >99% yield).

Embodiment 2

[0042] Example 2: Preparation of (s)-1-phenylethyl alcohol 2a from acetophenone 1a

[0043]

[0044] Under argon atmosphere, the above-mentioned catalyst (0.1%, 0.0025mmol), acetophenone 1a (300mg, 2.5mmol) and KOtBu (28mg, 0.25mmol) prepared by the preparation method of type A catalyst were dissolved in n-PrOH ( 2.5ml) and placed in a sealed tube. Use liquid nitrogen to freeze the solution in the sealed tube into a solid and evacuate the sealed tube into a vacuum with a vacuum pump, then heat the sealed tube to melt the solid inside and pour 1 atm of hydrogen into the sealed tube, and stir at room temperature for 30 h. After the reaction, the solvent was drained and separated by column chromatography (using a silica gel column; eluent: petroleum ether / ethyl acetate=5 / 1) to obtain pure product 2a. The product was a colorless liquid (96% ee, >99% yield).

Embodiment 3

[0045] Example 3: Preparation of (s)-1-phenylethyl alcohol 2a from acetophenone 1a

[0046]

[0047] Under an argon atmosphere, the above-mentioned catalyst (0.1%, 0.0025mmol), acetophenone 1a (300mg, 2.5mmol) and KO t Bu (28 mg, 0.25 mmol) was dissolved in n-PrOH (2.5 ml) and placed in an autoclave. Fill the autoclave with 20 atm hydrogen and stir at room temperature for 10 h. After the reaction, the solvent was drained and separated by column chromatography (using a silica gel column; eluent: petroleum ether / ethyl acetate=5 / 1) to obtain pure product 2a. The product was a colorless liquid (98% ee, >99% yield).

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PUM

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Abstract

The invention provides a chiral ruthenium catalyst, which has a relatively low cost but the same high efficiency. The catalyst is characterized in that a chiral diamine and an achiral phosphorus are used as ligands, and has a structural formula below. In the formula, NH=NH represents the chiral diamine, X and Y are negative ions, Ru is a metal ruthenium element and PR2=PR2 represents the achiral phosphorus ligand. The chiral ruthenium catalyst is used in the asymmetric hydrogenation of ketone and has very high activity and enantioselectivity.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a chiral metal ruthenium catalyst and its application in asymmetric hydrogenation of ketones. Background technique [0002] As the core technology of asymmetric synthesis, asymmetric hydrogenation reaction is one of the most concise, economical and efficient methods for the synthesis of chiral alcohols. Many natural products and physiologically active organic compounds contain the structure of chiral secondary alcohols. Chiral alcohols and chiral amino alcohols are important intermediates for the synthesis of chiral drugs, agricultural chemicals, spices and liquid crystals, and are also important precursors for many important compounds, such as halides, amino compounds, esters and ether compounds. At the same time, it can also be used as a chiral source or modified as a chiral ligand in asymmetric synthesis. It occupies an important position in chemical synt...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07B41/02C07C29/145C07C33/22C07C33/20C07C33/46C07C41/26C07C43/23C07D307/42C07D333/16C07C33/18C07C35/36C07C35/23C07C33/025C07C213/00C07C215/30C07D333/20
Inventor 黄汉民朱其明史登健夏春谷
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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