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Applications of chiral polymer catalyst in asymmetric reaction

A polymer and catalyst technology, applied in the field of preparation of heterogeneous catalysts, can solve the problems of difficult catalyst recovery, low activity of heterogeneous asymmetric reaction catalysts, etc., and achieve high stability, shortened reaction time, and optimized reaction activity.

Active Publication Date: 2017-06-16
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] In view of the above defects and improvement needs of the prior art, the present invention provides a preparation method and application of a chiral porous polymer, the purpose of which is to improve the catalytic activity and stability of heterogeneous asymmetric reactions by optimizing the synthesis raw materials and processes , in order to solve the problems of difficult recovery of existing homogeneous asymmetric reaction catalysts and low activity of heterogeneous asymmetric reaction catalysts

Method used

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  • Applications of chiral polymer catalyst in asymmetric reaction
  • Applications of chiral polymer catalyst in asymmetric reaction
  • Applications of chiral polymer catalyst in asymmetric reaction

Examples

Experimental program
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Effect test

Embodiment 2

[0037] Dissolve 5.0g of (S)-5,5'-divinyl-BINAP ligand in 50mL tetrahydrofuran solvent at 25°C under an inert gas atmosphere, add 50.0g of divinylbenzene monomer, stir well, then slowly add 0.5g free radical initiator azobisisobutyronitrile, stirred for 0.5h, then transferred the solution to a polytetrafluoro-lined kettle, and solvothermally polymerized at 100°C for 24h. After the reaction, the reaction product was vacuum-dried at 65° C. for 10 h to obtain a porous chiral polymer. Take 0.044g [RuCl 2 (benzene)] 2 Dissolve in 8mL of N,N-dimethylformamide solvent, add 2.4g of polymer material, and stir at 100°C for 3h under an inert gas atmosphere. Then vacuum dry at 75°C for 10 h. The heterogeneous catalyst 1 for the asymmetric reaction of β-keto esters was obtained.

Embodiment 3

[0039] In Example 3, except that 5.0g (S)-5,5'-divinyl-BINAP ligand was replaced by 5.0g (S)-4,4'-divinyl-BINAP ligand, the rest of the operations were the same as in Example 2 Similarly, catalyst 2 was prepared.

Embodiment 4

[0041] In Example 4, except that 5.0g (S)-5,5'-divinyl-BINAP ligand was replaced with 12.5g (S)-5,5'-divinyl-BINAP, the rest of the operations were the same as in Example 2, Catalyst 3 was prepared.

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Abstract

The invention discloses applications of a chiral polymer catalyst in asymmetric reaction, and belongs to the field of material synthesis and application. The phosphine-containing polymer is obtained via mixed polymerization of vinyl-containing chiral bidentate phosphine ligand BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) and derivative of vinyl-containing chiral bidentate phosphine ligand BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) with other vinyl comonomers. The vinyl polymer possesses relatively large specific surface area and porosity, and excellent thermal stability and chemical stability. In the heterogeneous catalyst, one or a plurality of elements selected from Ru, Rh, Ir, Pa, Au, and Cu are taken as active ingredients. The chiral ligand is uniformly embedded into and highly dispersed in a polymer skeleton, so that metal dispersion degree on the catalyst is relatively high, and relatively high catalytic activity is achieved. The heterogeneous catalyst is suitable for a plurality of reaction technology including intermittent still reaction, continuous fixed bed reaction, and trickle bed reaction. When the heterogeneous catalyst is used in catalytic kettle-type asymmetric hydrogenation, high target product yield is achieved, and enantioselectivity is higher than 96%.

Description

technical field [0001] The invention belongs to the field of heterogeneous catalysis, and is suitable for the preparation method of heterogeneous catalysts of chiral phosphine-containing organic polymers loaded with metals which are suitable for catalyzing the asymmetric hydrogenation reaction of β-keto esters. Background technique [0002] Asymmetric hydrogenation of unsaturated compounds containing carbon-carbon double bonds (C=C), carbon-oxygen double bonds (C=O) and carbon-nitrogen double bonds (C=N) with hydrogen molecules catalyzed by transition metal complexes Reaction is an important method for the synthesis of optically active compounds. This method is highly efficient, highly atom-economical, and environmentally friendly. After more than 40 years of development, asymmetric catalytic hydrogenation has been successfully applied to various types of chiral amino acids, chiral alcohols, chiral amines, and chiral carboxylic acids. Asymmetric Synthesis of Sexual Compound...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07C67/31C07C69/675C07C69/732
CPCB01J31/061B01J31/2452B01J2231/643B01J2531/0266B01J2531/821C07B2200/07C07C67/31C07C69/675C07C69/732
Inventor 丁云杰王涛吕元
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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