Method for catalyzing asymmetric Henry reaction of trifluoromethyl ketone

A technology of methyl and alkyl, which is applied in the field of catalyzing the asymmetric Henry reaction of trifluoromethyl ketone, which can solve problems such as complicated operation, low universality of trifluoromethyl ketone, and difficult preparation of catalysts

Active Publication Date: 2020-10-16
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] The technical problem to be solved by the present invention is that the asymmetric Henry reaction substrate of the existing catalyzed trifluoromethyl ketone has low universality, complicated operation, low reaction yield, low enantioselectivity and difficult preparation of the catalyst. For this reason, the invention provides a kind of method of catalytic trifluoromethyl ketone asymmetric Henry reaction

Method used

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  • Method for catalyzing asymmetric Henry reaction of trifluoromethyl ketone
  • Method for catalyzing asymmetric Henry reaction of trifluoromethyl ketone
  • Method for catalyzing asymmetric Henry reaction of trifluoromethyl ketone

Examples

Experimental program
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Effect test

Embodiment 1

[0194] Put (D)-serine methyl ester hydrochloride (10.0g, 64mmol, 1.0equiv.,) into the three-necked flask, dissolve it in 150mL1,2-dichloroethane, add triethylamine (16.0g, 2.5equiv.,) , after which TrtCl (15.4 g, 1.0 equiv.) was added in portions. Then, the reaction system was heated and stirred in an oil bath at 50° C. for 12 hours. TLC detected that the reactant completely disappeared, and the reaction system was placed in an ice-water bath. When the internal temperature reached 10°C, the reaction was quenched by slowly adding saturated ammonium chloride aqueous solution dropwise. The chloroform layer was separated, washed with saturated brine, dried by adding anhydrous sodium sulfate, filtered to obtain the organic phase, evaporated to remove the solvent, and recrystallized in a mixed solvent of petroleum ether / ethyl acetate to obtain 22.38 g of a white solid (compound A). Yield 97%.

Embodiment 2

[0196] Dissolve 22.38g (62mmol, 1.0eq.) of the amino-protected product (Compound A) in dichloromethane, cool the system to 0°C, and drop triethylamine (2.5eq., 11.0mL) and MsCl (1.5 equiv., 3.7mL), the dropwise addition was completed, and the ice-salt bath was removed, and the system naturally returned to room temperature and stirred for 24 hours. TLC detected that the reactant completely disappeared, and added deionized water to quench the reaction, and then separated to obtain a dichloromethane layer. Wash with saturated brine, add anhydrous sodium sulfate to dry, distill off the solvent, and recrystallize in a mixed solvent of n-hexane / methyl tert-butyl ether to obtain 20.9 g of white solid (compound B), yield 98%.

Embodiment 3

[0198] Under the protection of argon, add 3.0g (125mmol, 2.1eq.) of metal magnesium and 20.0mL of THF into a three-necked flask, add 1 grain of iodine to catalyze, and then slowly add a THF solution of 15.7g (125mmol, 2.1eq.) of bromobenzene (40.0mL) to keep the system in a slightly boiling state. After the dropwise addition was completed, reflux was continued for 1.5 hours. Then the system was cooled to 0°C in an ice-water bath, and a THF solution (50.0 mL) of 20.9 g (61 mmol, 1 eq.) of the ring-closing product (compound B) was slowly added dropwise. After the addition was complete, the system was returned to room temperature and continued to stir for 4 Hour. After TLC detects that the reactant completely disappears, quench the reaction by adding saturated ammonium chloride aqueous solution under ice-water bath cooling, extract three times with ethyl acetate, separate the organic layer, wash with saturated brine, dry over anhydrous sodium sulfate, and evaporate the solvent ...

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Abstract

The invention provides a method for catalyzing asymmetric Henry reaction of trifluoromethyl ketone. The method adopts a brand-new catalyst namely a compound shown as a formula I, and is simple to operate, high in substrate universality, high in reaction yield and high in enantioselectivity.

Description

technical field [0001] The invention relates to a method for catalyzing the asymmetric Henry reaction of trifluoromethyl ketone. Background technique [0002] The Henry reaction refers to an organic chemical reaction in which a nitro compound with α-active hydrogen undergoes nucleophilic addition to the carbonyl of an aldehyde or ketone under the action of a base to form a β-nitro alcohol. Since the Shibasaki group first reported the asymmetric Henry reaction catalyzed by metal complexes in 1992, the research on the asymmetric Henry reaction has attracted great attention from workers in the field of chemistry, because the chiral β-nitroalcohols generated by the reaction can undergo organic transformation A variety of organic molecular skeletons with biological activity and pharmaceutical value can be synthesized, so this reaction has a very wide range of applications in organic synthesis. [0003] Asymmetric Henry reactions can usually be realized through three catalytic mo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C275/40C07C273/18C07D295/125B01J31/02C07C205/16C07C205/31C07C201/12
CPCB01J31/0249C07C201/12C07C275/40C07D295/125C07C205/16C07C205/31
Inventor 赵刚孟翔宇陆颖鹏花文杰张钧康张亚竹
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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