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Synthesis method and application of thiopheneamide-substituted chiral phosphine ferrocene catalyst

A synthesis method and technology of thiophene amide, applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., to achieve mild reaction conditions, good stability, and low dosage Effect

Active Publication Date: 2015-10-14
沈阳钢中宝科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] However, there are few studies on the asymmetric [3+2] cycloaddition reaction catalyzed by bifunctional chiral phosphine small molecules with ferrocene as the backbone. The goal

Method used

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  • Synthesis method and application of thiopheneamide-substituted chiral phosphine ferrocene catalyst
  • Synthesis method and application of thiopheneamide-substituted chiral phosphine ferrocene catalyst
  • Synthesis method and application of thiopheneamide-substituted chiral phosphine ferrocene catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0047] Add thiophene-2-carboxylic acid (0.096g, 0.75mmol), DCC (0.155g, 0.75mmol), dichloromethane (10mL) and (1S)-diphenylphosphino-(2R) into a 50mL two-necked flask successively. -Aminoethylferrocene(II) (0.207g, 0.5mmol), react at 20°C for 2 hours, add 15mL of water and stir for 30 minutes, filter with suction, pour the filtrate into a separatory funnel to separate the organic layer and the water layer Extracted 3 times with dichloromethane, washed 3 times with saturated brine, combined organic phase, anhydrous Na 2 SO 4 Drying and concentration under reduced pressure gave the crude product, which was subjected to column chromatography (petroleum ether: ethyl acetate = 15:1, V:V) to obtain 0.227 g of a yellow solid with a yield of 86.8%, m.p.70.1-71.4°C; [α] 20 D =-344.1°(c 1.0, CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ7.57–7.51(m,2H),7.44(dd,J=4.0,1.2Hz,1H),7.40(dd,J=5.2,1.2Hz,4H),7.33(dd,J=0.8,2.8Hz ,1H),7.21–7.16(m,5H),7.02(dd,J=5.2,3.6Hz,1H),5.27(m,1H),4.53(d,J=0.8Hz,...

Embodiment 2

[0049] Add thiophene-2-carboxylic acid (0.096g, 0.75mmol), DCC (0.103g, 0.5mmol) and anhydrous dichloromethane (5mL) successively into a 50mL two-necked flask, place in an ice bath, stir magnetically, and protect with nitrogen , the system was white suspension. After the temperature of the system was constant, a mixture of (1S)-diphenylphosphino-(2R)-aminoethylferrocene(II) (0.207g, 0.5mmol) and 5mL of anhydrous dichloromethane was slowly added dropwise, After dripping, move the reaction bottle to 30°C for reaction, TLC detects the reaction until the raw material (II) disappears, add 15mL water to quench the reaction, filter with suction, separate the white solid, pour the filtrate into the separatory funnel to separate the organic layer, water layer was extracted 3 times with dichloromethane, washed 3 times with saturated brine, and the organic phases were combined, anhydrous Na 2 SO 4 Drying; filtration and rotary evaporation to obtain the crude product, which was subjecte...

Embodiment 3

[0051] Add thiophene-2-carboxylic acid (0.096g, 0.75mmol), DCC (0.206g, 1.0mmol) and anhydrous dichloromethane (5mL) successively into a 50mL two-necked flask, place in an ice bath, stir magnetically, and protect with nitrogen . After the temperature of the system was constant, a mixture of (1S)-diphenylphosphino-(2R)-aminoethylferrocene(II) (0.207g, 0.5mmol) and 5mL of anhydrous dichloromethane was slowly added dropwise, After dripping, move the reaction bottle to 20°C for reaction, TLC detects the reaction until the raw material (II) disappears, add 15mL water to quench the reaction, filter with suction, separate the white solid, pour the filtrate into the separatory funnel to separate the organic layer, water layer was extracted 3 times with dichloromethane, washed 3 times with saturated brine, and the organic phases were combined, anhydrous Na 2 SO 4 Drying; the crude product was obtained by suction filtration and rotary evaporation, and 0.209 g of a yellow solid was obt...

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Abstract

The invention discloses a thiopheneamide-substituted chiral phosphine ferrocene derivative represented by a formula (I). A preparation method of the derivative comprises the following steps: (1S)-diphenylphosphino-(2R)-aminoethyl ferrocene represented by a formula (II) and thiophenecarboxylic acid represented by a formula (III) are adopted as raw materials, and are miscibility dissolved in an organic solvent A; N,N'-di(cyclohexyl)carboimide (DCC) is adopted as a catalyst, and a reaction is carried out for 1-4h under a temperature of 0-40 DEG C; and a reaction mixture is subjected to a post-treatment, such that thiopheneamide-substituted chiral phosphine ferrocene represented by the formula (I) is obtained. The compound can be used as a catalyst for an asymmetric [3+2] cycloaddition reaction. The catalyst has high catalytic activity and good stability. The method has the advantages of mild reaction conditions and good yield, and has a good application prospect.

Description

(1) Technical field [0001] The invention relates to a synthesis method of chiral phosphinoferrocene substituted by thiophene amide, and it is used as a catalyst for promoting asymmetric [3+2] cycloaddition reaction involving Morita-Baylis-Hillman carbonate. (2) Technical background [0002] The [3+2] cycloaddition reaction is an efficient method for constructing complex structures such as double five-membered rings, five-membered heterocycles, and biologically active compounds. In recent years, chiral phosphine-catalyzed asymmetric [3+2] cycloaddition reactions have become a research hotspot for chemists. Common phosphine-containing catalysts that catalyze [3+2] cycloaddition reactions can be divided into two categories: monochiral phosphine catalytic systems (as shown in formulas A and C), bifunctional chiral phosphine systems (as shown in formula B Show). [0003] [0004] In 1997, Zhang et al first applied the chiral cyclic phosphine [2,2,1] hexane derivative A to th...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02B01J31/24C07D209/52
CPCB01J31/2295C07D209/52C07F17/02
Inventor 钟为慧胡海文苏为科
Owner 沈阳钢中宝科技有限公司
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