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Phenol derivative containing (Rp)-2-chiral phosphinate substituent and preparation method thereof

A phosphinate and substituent technology, applied in the field of asymmetric catalysis synthesis, can solve the problems of difficult recovery and utilization of chiral resolving agents, low activity and selectivity of resolving agents, cumbersome experimental steps, etc., and achieves good industrial application. Prospects, cheap catalysts, and the effect of simple and easy methods

Active Publication Date: 2013-09-25
HUNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these methods generally use relatively expensive chiral catalysts, and the experimental steps are cumbersome, the reaction conditions are harsh, and the yield is low; even if some chiral resolution methods are used, the activity and selectivity of the resolving agent are generally low. Moreover, chiral resolution reagents are difficult to recycle

Method used

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  • Phenol derivative containing (Rp)-2-chiral phosphinate substituent and preparation method thereof
  • Phenol derivative containing (Rp)-2-chiral phosphinate substituent and preparation method thereof
  • Phenol derivative containing (Rp)-2-chiral phosphinate substituent and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Take 2.80 g (10 mmol) ( R p)-Phenylphosphinate-(-)-menthol ester, 1.034 g (11 mmol) phenol, 50 mL carbon tetrachloride and 2.78 mL (20 mmol) triethylamine were added to a round bottom flask under nitrogen atmosphere , stirred at room temperature for 12 h to obtain the target product R p-(-)-menthol- O -Phenyl-phenylphosphinate, the yield is 99%; take 1.86 g (5 mmol) R p-(-)-menthol- O -Phenyl-phenylphosphinate, added to 25 mL tetrahydrofuran solution under nitrogen atmosphere, and heated at -78 o Slowly add this solution dropwise to the mixed solution of lithium diisopropylamide (5.5 mmol)-tetrahydrofuran (25 mL) at ℃, and then under the condition of stirring from minus 78 o C was warmed up to room temperature and continued to react for 6 h to obtain the target product R p-(-)-menthol-2-hydroxyphenyl-phenylphosphinate in 99% yield.

[0034]

Embodiment 2

[0036] Take 2.80 g (10 mmol) (R p)-Phenylphosphinate-(-)-menthol ester, 0.9494 g (10.1 mmol) phenol, 40 mL toluene, 10 mL carbon tetrachloride, and 6.52 g (20 mmol) cesium carbonate were added to the round bottom under nitrogen atmosphere In the flask, stir the reaction at room temperature for 12 h to obtain the target product R p-(-)-menthol- O -Phenyl-phenylphosphinate, the yield is 91%; take 1.86 g (5 mmol) R p-(-)-menthol- O -Phenyl-phenylphosphinate, added to 25 mL tetrahydrofuran solution under nitrogen atmosphere, and heated at -78 o Slowly add this solution dropwise to the mixed solution of lithium diisopropylamide (6.5 mmol)-tetrahydrofuran (25 mL) at ℃, and then under the condition of stirring from minus 78 o C was warmed up to room temperature and continued to react for 6 h to obtain the target product R p-(-)-menthol-2-hydroxyphenyl-phenylphosphinate in 99% yield.

[0037]

Embodiment 3

[0039] Take 2.80 g (10 mmol) ( R p)-Phenylphosphinate-(-)-menthol ester, 1.015 g (10.8 mmol) phenol, 40 mL acetonitrile, 10 mL carbon tetrachloride and 4.24 g (20 mmol) potassium phosphate were added to the circle under nitrogen atmosphere Bottom flask, stirred at room temperature for 12 h to obtain the target product R p-(-)-menthol- O -Phenyl-phenylphosphinate, the yield is 82%; take 1.86 g (5 mmol) R p-(-)-menthol- O -Phenyl-phenylphosphinate, added to 25 mL tetrahydrofuran solution under nitrogen atmosphere, and heated at -78 o Slowly add this solution dropwise to the mixed solution of lithium diisopropylamide (7.5 mmol)-tetrahydrofuran (25 mL) at ℃, and then under the condition of stirring from minus 78 o C was warmed up to room temperature and continued to react for 6 h to obtain the target product R p-(-)-menthol-2-hydroxyphenyl-phenylphosphinate in 99% yield.

[0040]

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Abstract

The invention provides a method for synthesizing a phenol derivative having a phosphorous chiral center and containing a (Rp)-2-chiral phosphinate substituent in a high stereoselectivity manner. According to the method, with small organic molecules as a catalyst and a (Rp)-2-chiral phosphinate compound containing P-H bonds, and phenol as reaction substrates, an organic solvent is added into a reaction system. The method has the advantages that the catalyst is low in cost and easy to obtain; reaction conditions are mild, safe and reliable; the stereoselectivity of the obtained target product is close to 100 percent and the yield of the obtained target product is up to 90 percent. According to the method provided by the invention, the defects of poor stereoscopic enantioselectivity, fussy reaction steps, low yield and the like of an organic phosphine compound containing the phosphorous chiral center, which is synthesized by adopting a traditional method, are overcome, and the method has a favorable industrial prospect. The invention further provides the phenol derivative having the phosphorous chiral center and containing the (Rp)-2-chiral phosphine substituent.

Description

[0001] 【Technical field】 [0002] The invention relates to the field of asymmetric catalytic synthesis of organic phosphine compounds containing a phosphorus chiral center, in particular to a compound containing a phosphorus chiral center ( R Phenol derivatives of p)-2-chiral phosphinate substituents and methods for their preparation. [0003] 【Background technique】 [0004] Organic (phosphino)phosphonate compounds with phosphorus chiral centers are an important class of organic compounds, which have good optical activity and biological activity, making them useful in biology, medicine, optically active materials and asymmetric catalytic synthesis. and so on have a wide range of applications. However, it is difficult to find natural optically active chiral organophosphorus compounds in nature, and most of the known organophosphorus compounds with phosphorus chiral centers are synthesized by chemical methods. [0005] In recent years, with the continuous expansion of the a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/32
Inventor 尹双凤熊碧权周永波韩立彪
Owner HUNAN UNIV
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