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Organic small molecule catalyst of aqueous phase asymmetric direct aldol condensation reaction, and preparing method and use thereof

An aldol condensation reaction and catalyst technology, applied in the field of organic small molecule chiral catalysts, can solve the problems of being unfriendly to the environment, unsatisfactory results, and the catalyst cannot simultaneously obtain high yields, etc., and achieve the effect of high yields

Inactive Publication Date: 2007-08-08
CHENGDU ORGANIC CHEM CO LTD CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these two catalysts are only suitable for the reaction between acetone and aldehyde, and the results are not satisfactory when cyclohexanone is used as the substrate.
Xiao Wenjing and others reported that another class of proline amide derivatives can well catalyze the asymmetric direct aldol condensation reaction between cyclohexanone and aldehyde, but the solvent they use is chloroform, which is not environmentally friendly. process, and high selectivity can only be obtained at low temperature (Org.Lett.2005, 7, 4543)
For the needs of green chemistry, some organic small molecule catalysts have been designed and found to catalyze the reaction between cyclohexanone and aldehyde in aqueous phase, but these catalysts cannot simultaneously obtain high yield, diastereoselectivity and Optical selectivity (Angew.Chem.Int.Ed.2006, 45, 958: J.Am.Chem.Soc.2006, 128, 734: Chem.Commun.2006, 2801)

Method used

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  • Organic small molecule catalyst of aqueous phase asymmetric direct aldol condensation reaction, and preparing method and use thereof
  • Organic small molecule catalyst of aqueous phase asymmetric direct aldol condensation reaction, and preparing method and use thereof
  • Organic small molecule catalyst of aqueous phase asymmetric direct aldol condensation reaction, and preparing method and use thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Preparation and resolution of N-benzyloxycarbonyl-protected catalyst precursors

[0026] Dissolve 3.98 g of L-form proline protected by benzyloxycarbonyl and 1.62 g of triethylamine in 30 mL of tetrahydrofuran solution, and cool to 0 degrees Celsius in an ice-water bath. Under the condition of stirring, 0.88 g of ethyl chloroformate was added dropwise, and stirring was continued for 30 minutes after the dropwise addition was completed. 4.56 g of racemic binaphtholamine was dissolved in 100 mL of THF, and added dropwise to the reaction mixture. After the dropwise addition, the reaction was continued at 0°C for 1 hour, and then at room temperature for 24 hours. After the reaction stopped, the solid was filtered off, and the solvent was distilled off under reduced pressure on a rotary evaporator. The resulting substance was subjected to flash column chromatography with silica gel H, and the developing solvent was petroleum ether: ethyl acetate=2:1, and the configuration ...

Embodiment 2

[0028] Preparation of Catalyst 1a

[0029] Add 2g of Z-1a obtained from Example 1, 0.4g of 10% Pd / C and 60ml of methanol into a 100ml two-necked flask, feed 1atm of hydrogen under reflux at 40°C, and stir for 1 hour. After the reaction was finished, the solid was filtered off, and the resulting solution was evaporated to dryness and recrystallized with dichloromethane to obtain the catalyst 1a.

[0030] Melting point: 240-241℃; specific rotation value: [] 20 D =-23.46 (c=0.5, THF); NMR analysis: (600MHz, CDCl 3 ) (ppm) 1.22-1.28 (m, 2H) 1.46-1.50 (m, 1H) 1.67-1.72 (m, 1H) 1.83-1.88 (m, 1H) 2.33-2.35 (m, 1H) 3.56-3.58 (m, 1H) 5.29 (s, 1H) 7.02-7.04 (d, 1H, J = 8.5Hz) 7.22-7.25 (m, 1H) 7.29-7.39 (m, 3H) 7.38-7.39 (d, 1H, J = 8.88Hz) 7.42-7.44 (m, 1H) 7.87-7.88 (d, 1H, J = 8.2Hz) 7.92-7.97 (dd, 2H, J = 8.2, J = 8.88) 8.04-8.06 (d, 1H, J = 8.9Hz) 8.80-8.82 (d, 1H, J=8.9Hz) 9.76 (s, 1H); 13 CNMR (600MHz, CDCl 3 )(ppm)25.36,30.68,46.23,60.70,113.62,116.90,117.74,119.82,123.82...

Embodiment 3

[0032] Preparation of Catalyst 1b

[0033] Add 2g of Z-1b obtained from Example 1, 0.4g of 10% Pd / C and 60ml of methanol into a 100ml two-neck flask, feed 1atm of hydrogen under reflux at 40°C, and stir for 1 hour. After the reaction was finished, the solid was filtered off, and the resulting solution was evaporated to dryness and recrystallized with a mixed solvent of petroleum ether and tetrahydrofuran to obtain catalyst 1b.

[0034] Melting point: 236-237℃; Specific rotation value: [] 20 D =-7.88 (c=0.5, THF); NMR analysis: 1 HNMR (600MHz, CDCl 3 ) (ppm) 1.21-1.23 (m, 1H) 1.36-1.46 (m, 1H) 1.48-1.52 (m, 1H) 1.80-1.85 (m, 1H) 1.91-1.97 (m, 1H) 2.24-2.27 (m, 1H) 2.57-2.61 (m, 1H) 3.53-3.56 (dd, 1H, J = 9.4, J = 4.1) 5.29 (s, 1H) 7.01-7.03 (d, 1H, J = 8.5) 7.23-7.28 (m, ( d, 1H, J=8.9) 8.66-8.67 (d, 1H, J=8.9); 13 CNMR (600MHz, CDCl 3 )(ppm)25.69,30.71,46.69,60.68,113.88,117.78,118.18,120.45,123.70,124.36,125.25,127.09,127.18,128.23,128.31,129.35,130.26,130.65,131.19,133...

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Abstract

The invention discloses an organic molecular catalyst of water-phase asymmetrical hydroxy-aldehyde condensing reaction, which is characterized by the following: possessing central chirality and axial chirality to catalyze asymmetrical hydroxy-aldehyde condensing reaction in the water phase; improving receiving rate; obtaining the product with diastereomer selectivity and high-optical purity.

Description

technical field [0001] The invention belongs to the field of asymmetric catalysis of organic chemistry, in particular to an organic small molecule chiral catalyst used for direct aldol condensation reaction in water phase. Background technique [0002] The aldol condensation reaction is one of the most important reactions in organic chemistry for the formation of C-C bonds. Highly functionalized products can be obtained through aldol condensation reactions and generate new chiral centers. In the synthesis of complex molecules and the preparation of optically active small molecule building blocks, many examples of asymmetric aldol condensations can be found (Comprehensive Organic Synthesis; Pergamon Press: NewYork, 1991: J.Am.Chem.Soc.1981, 103, 2127: J. Am. Chem. Soc. 1989, 111, 5493: J. Am. Chem. Soc. 1997, 119, 2586). In the reaction of asymmetric aldol condensation, the catalyzed direct asymmetric aldol condensation reaction has become a research hotspot in recent years...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C45/72C07C49/17C07B53/00
Inventor 蒋毅王超张小霞张国林李伯刚
Owner CHENGDU ORGANIC CHEM CO LTD CHINESE ACAD OF SCI
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