Method for using palladium homogeneous system in enantioselective catalysis of ketone hydride

A technology for catalytic hydrogenation of ketones and catalysts, which is applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., to achieve the effects of convenient preparation, easy availability of raw materials, and good yield

Inactive Publication Date: 2007-01-24
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0011] However, so far, there are few examples of asymmetric hydrogenation using palladium in homogeneous systems

Method used

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  • Method for using palladium homogeneous system in enantioselective catalysis of ketone hydride
  • Method for using palladium homogeneous system in enantioselective catalysis of ketone hydride
  • Method for using palladium homogeneous system in enantioselective catalysis of ketone hydride

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Embodiment 1: optimization of conditions

[0039] Put palladium precursor (0.005 mmol) and chiral ligand (0.006-0.0075 mmol) into a reaction bottle, add 1 ml of acetone after nitrogen replacement, and stir at room temperature for 1 hour. Then concentrate in vacuo, add 1-1.2 milliliters of 2,2,2-trifluoroethanol under nitrogen, transfer this solution to the reaction kettle with the substrate (0.25 mmol) in advance, and feed hydrogen (14-70 atmospheric pressure) , and put it into an oil bath of specified temperature to react for 12 hours. Slowly release hydrogen, remove the solvent, and directly separate the pure product by column chromatography. The reaction formula and ligand structure are as follows:

[0040]

[0041] The conversion rate was determined by proton nuclear magnetic resonance spectroscopy, and the enantiomeric excess of the product was determined by chiral HPLC, see Table 2.

[0042] serial number

Embodiment 2

[0043] Example 2: Asymmetric hydrogenation of α-o-benzamide substituted ketones

[0044] Pd(CF 3 CO 2 ) 2 (1.7 mg, 0.005 mmol) and the chiral bisphosphorus ligand (R, R)-Me-DuPhos (1.8 mg, 0.006 mmol), after nitrogen replacement, 1 ml of acetone was added and stirred at room temperature for 1 hour. Then concentrate in vacuo, add 1-1.2 milliliters of 2,2,2-trifluoroethanol under nitrogen, transfer this solution to the reaction kettle with the substrate (0.25 mmol) in advance, and feed hydrogen (14-28 atmospheric pressure) , Put it into the specified temperature oil bath to react for 12-18 hours. Slowly release the hydrogen, remove the solvent and obtain the pure product directly by column chromatography, the reaction formula is as follows:

[0045]

[0046] The catalyst used in No. 5 is Pd(OTf) 2 / (S)-SYNPHOS pure complex, the enantiomeric excess of the product was determined by chiral HPLC, see Table 3.

[0047] serial number

Embodiment 3

[0048] Example 3: Asymmetric hydrogenation of additionally functionalized ketones

[0049] Pd(CF 3 CO 2 ) 2 (1.7mg, 0.005mmol) and chiral bisphosphorus ligand (0.006-0.0075mmol), add 1ml of acetone after nitrogen replacement, and stir at room temperature for 1 hour. Then concentrate in vacuo, add 1-1.2 milliliters of 2,2,2-trifluoroethanol under nitrogen, transfer this solution to the reaction kettle with the substrate (0.25 mmol) in advance, feed hydrogen to the specified pressure, and put Reaction in an oil bath at specified temperature for 12-18 hours. Slowly release the hydrogen, remove the solvent and obtain the pure product directly by column chromatography, the reaction formula is as follows:

[0050]

[0051] The enantiomeric excess of the product was determined by chiral HPLC or GC, see Table 4.

[0052] Table 4: Asymmetric hydrogenation of functionalized ketones

[0053]

[0054] 9

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Abstract

The method of catalyzing hydrogenation of ketone enantioselectively with homogeneous Pt catalyst system has chiral diphosphorus complex of Pt as catalyst system, reaction temperature of 25-75deg.c, solvent of 2, 2, 2-trifluoroethanol, reaction pressure of 3-70 atm and chiral diphosphorus ligand used. The homogeneous Pt catalyst system is prepared through mixing metal precursor of Pt and chiral diphosphorus ligand at room temperature and the subsequent vacuum concentrating. The catalyst can result in asymmetrical inducing as high as 92 % on alpha-one-benzamide substituted ketone. The present invention has simple operation, facile material, high reaction selectivity, high yield and environment friendship.

Description

technical field [0001] The invention relates to a method for catalyzing the hydrogenation of ketones with high enantioselectivity using a palladium homogeneous system. technical background [0002] Asymmetric hydrogenation has many advantages: very high catalyst activity, fast reaction speed, convenient separation of products, less side reactions, etc. The use of chiral catalysts to catalyze asymmetric hydrogenation reactions has made great achievements. Among them, chiral catalysts are divided into two types: homogeneous and heterogeneous chiral catalysts. [0003] Homogeneous chiral catalysts are soluble metal complexes with chiral ligands, which interact with metal center ions to generate a chiral atmosphere, which is the active center of asymmetric catalysis. The metals of the homogeneous catalytic system currently used in asymmetric hydrogenation are mainly rhodium, ruthenium and iridium, which can be divided into the following five categories: [0004] A rhodium cata...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24
Inventor 周永贵汪游清卢胜梅
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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