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Enantioselective method for synthesizing beta-ester-gamma-butyrolactone

A technology of enantioselectivity and butyrolactone, which is applied in the chemical industry, can solve the problems of no enantioselectivity or the limitation of the synthesis process, and achieve the effect of high yield, high selectivity and simple synthesis steps

Active Publication Date: 2015-10-07
DALIAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] In summary, the above-mentioned synthetic methods have the limitation of not having enantioselectivity or complicated synthetic process.

Method used

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  • Enantioselective method for synthesizing beta-ester-gamma-butyrolactone
  • Enantioselective method for synthesizing beta-ester-gamma-butyrolactone
  • Enantioselective method for synthesizing beta-ester-gamma-butyrolactone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Under nitrogen atmosphere, add CuF(PPh 3 ) 3 · 2MeOH (17.3 mg, 0.0185 mmol), (S)-BINAP (17.5 mg, 0.0281 mmol), toluene (6 mL), stirred at 20° C. for 30 min. Join (CH 3 ) 3 Si(OSiHMe) r OSi(CH 3 ) 3 (PMHS) (mean value of r = 30, 0.10 mL, 1.67 mmol), stirred for 30 min. A mixture of acetophenone (0.070 mL, 0.60 mmol) and dimethyl maleate (0.10 mL, 0.78 mmol) (1 mL of toluene) was added. After reacting for 1h, add 5mL of 1.5M NH 4 F solution (5 mL), stirred for 0.5 h. Remove the insoluble matter by filtration with diatomaceous earth, wash the filter cake with dichloromethane, separate the phases of the filtrate, extract the aqueous phase with dichloromethane (3×5mL), wash the combined organic phase with saturated brine, and wash the organic phase with Dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by column to obtain β-methoxyl-γ-methyl-γ-phenyl-γ-butyrolactone (0.138g), with a yield of 98%. The content of each isomer was a...

Embodiment 2

[0052] Under nitrogen atmosphere, add CuF(PPh 3 ) 3 · 2MeOH (5.6 mg, 0.0060 mmol), (S)-BINAP (5.6 mg, 0.0060 mmol), toluene (10 mL), stirred at 20° C. for 30 min. PMHS (average value of r=30) (0.10 mL, 1.67 mmol) was added and stirred at 0° C. for 40 min. A mixture of acetophenone (0.070 mL, 0.60 mmol) and dimethyl maleate (0.10 mL, 0.78 mmol) (1 mL of toluene) was added. After reacting for 1h, add 5mL of 1.5M NH 4 F solution (5 mL), stirred for 0.5 h. Remove the insoluble matter by filtration with diatomaceous earth, wash the filter cake with dichloromethane, separate the phases of the filtrate, extract the aqueous phase with dichloromethane (3×5mL), wash the combined organic phase with saturated brine, and wash the organic phase with Dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by column to obtain β-methoxyl-γ-methyl-γ-phenyl-γ-butyrolactone (0.136g), with a yield of 97%. The content of each isomer was analyzed by chiral GC, ee ...

Embodiment 3

[0054] Under nitrogen atmosphere, add CuF(PPh 3 ) 3 · 2MeOH (5.6 mg, 0.0060 mmol), (S)-BINAP (5.6 mg, 0.0060 mmol), THF (2 mL), stirred at 20° C. for 30 min. PMHS (average value of r=30) (0.10 mL, 1.67 mmol) was added and stirred at 40° C. for 40 min. The temperature was raised to 60° C., and a mixture (1 mL THF) of acetophenone (0.070 mL, 0.60 mmol) and dimethyl maleate (0.10 mL, 0.78 mmol) was added. React for 1h, add NH 4 F solution (5 mL), stirred for 0.5 h. Remove the insoluble matter by filtration with diatomaceous earth, wash the filter cake with dichloromethane, separate the phases of the filtrate, extract the aqueous phase with dichloromethane (3×5mL), wash the combined organic phase with saturated brine, and wash the organic phase with Dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and separated by column to obtain β-methoxyl-γ-methyl-γ-phenyl-γ-butyrolactone (0.127g), with a yield of 91%. The content of each isomer was analyzed by chir...

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Abstract

The invention relates to an enantioselective method for synthesizing beta-ester -gamma-butyrolactone, belonging to the technical field of chemical industry. The method comprises the following steps: by using silane, maleate or itaconate, and aldehyde or ketone as reactants, continuously carrying out tandem reactions by using a Cu-chiral phosphine catalyst in an organic solvent, and stirring to react at 0-60 DEG C for 0.25-10 hours to synthesize the chiral beta-ester -gamma-butyrolactone. Compared with the prior art, the method provided by the invention has enantioselectivity, the ee value of the product is up to 92%, and the diastereomer ratio is up to 18:82. The method has the advantages of simple steps and low cost. The obtained target compound has important bioactivities, such as antiinflammation activity, antitumor activity and the like. The method has potential application value.

Description

technical field [0001] The invention belongs to the technical field of chemical industry, and relates to a method for selectively synthesizing β-ester group-γ-butyrolactone with enantiomers. Background technique [0002] The structure of γ-butyrolactone exists in the natural products of paraconic acids, and it is also an important synthetic intermediate for the synthesis of natural products with the structure of γ-butyrolactone. [0003] Saconic acid (β-carboxy-γ-butyrolactone, such as structural formula 1) compounds are a class of compounds extracted from lichens, mosses and fungi, and are characterized in that the β-position of γ-butyrolactone is connected with a carboxyl group , a hydrocarbon group with 5-10 carbon atoms attached to the γ position. Many compounds with this type of structure have good biological activities such as antifungal, anti-inflammatory, and anti-tumor. The substituents on the γ-butyrolactone skeleton and the absolute configuration are of great si...

Claims

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Application Information

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IPC IPC(8): C07D307/33C07D307/34
CPCC07D307/33C07D307/34
Inventor 李争宁李志强姜岚干苗苗李增厂
Owner DALIAN UNIVERSITY
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