Method for synthesizing fluoro nitrogen heterocyclic compound

A heterocyclic compound and fluorinated technology, applied in organic chemical methods, chemical instruments and methods, organic halogenation, etc., to achieve high yield, good selectivity, and simple steps

Inactive Publication Date: 2010-04-07
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

However, currently, such fluorinated nitrogen-containing heterocycles are synthesized through classical fluorination reactions, such as the fluorination of alcohols using DAST, but there are selectivity problems in this reaction.

Method used

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  • Method for synthesizing fluoro nitrogen heterocyclic compound
  • Method for synthesizing fluoro nitrogen heterocyclic compound

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0015] Example 1: Synthesis

[0016] 4.5mg (0.02mmol) of Pd(OAc) 2 , 162.5mg (0.4mmol) of PhI (OCO t Bu) 2 , 125.9mg (1.0mmol) of AgF, 100mg of MgSO 4 and olefins 53.4mg (0.2mmol) was added to the reaction tube, then 1ml of anhydrous acetonitrile was added, and stirred at room temperature for 24 hours. Then filter, the solid was washed with dichloromethane, the combined filtrate was concentrated, and column chromatography was used to obtain 47.9 mg of product with gradient elution of ethyl acetate and petroleum ether The yield was 84%.

[0017] 1 H NMR (400M, CDCl 3 , TMS), δ7.65(d, J=8.0Hz, 2H), 7.34(d, J=8.0Hz, 2H), 4.77(dm, J=47.6Hz, 1H), 3.61(ddd, J=13.6, 11.2, 3.6Hz, 1H), 2.62(ddd, J=11.2, 7.6, 7.6Hz, 1H), 2.97(d, J=11.2Hz, 1H), 2.44(s, 3H), 2.38(d, J=11.2 Hz, 1H), 1.72(ddd, J=16.8, 13.2, 4.0Hz, 1H), 1.35(ddd, J=12.8, 12.8, 8.8Hz, 1H), 1.03(d, J=3.6Hz, 6H). 13 C NMR (100M, CDCl 3 ), δ143.66, 133.24, 129.70, 127.45, 85.55(d, J=231.9Hz), 56.58(d, J=1.5Hz), 49...

example 2

[0018] Example 2: Synthesis of (without MgSO4)

[0019] 4.5mg (0.02mmol) of Pd(OAc) 2 , 162.5mg (0.4mmol) of PhI (OCO t Bu) 2 , 125.9 mg (1.0 mmol) of AgF, alkene 53.4mg (0.2mmol) was added to the reaction tube, then 1ml of anhydrous acetonitrile was added, and stirred at room temperature for 24 hours. Then filter, the solid is washed with dichloromethane, the combined filtrates are concentrated, column chromatography, and gradient elution with ethyl acetate and petroleum ether to obtain 39 mg of product The yield is 69%.

Embodiment 3

[0020] Example 3: Synthesis

[0021] 4.5mg (0.02mmol) of Pd(OAc) 2 , 162.5mg (0.4mmol) of PhI (OCO t Bu) 2 , 125.9mg (1.0mmol) of AgF, 100mg of MgSO 4 and olefins 59.7mg (0.2mmol) was added to the reaction tube, then 1ml of anhydrous acetonitrile was added, and stirred at room temperature for 24 hours. Then filter, the solid was washed with dichloromethane, the combined filtrate was concentrated, and column chromatography was used to obtain 46.8 mg of product with ethyl acetate and petroleum ether gradient washing method The yield was 74%.

[0022] 1 H NMR (400M, CDCl 3 , TMS), δ8.39(d, J=8.8Hz, 2H), 7.96(d, J=8.8Hz, 2H), 4.80(dm, J=47.2Hz, 1H), 3.56(ddd, J=16.0, 11.6, 4.0Hz, 1H), 2.97(d, J=11.6Hz, 1H), 2.89(ddd, J=11.6, 7.6, 7.6Hz, 1H), 2.61(d, J=12.0Hz, 1H), 1.71( ddd, J=20.4, 13.6, 4.0Hz, 1H), 1.46(ddd, J=12.8, 12.8, 8.0Hz, 1H), 1.03(s, 6H). 13 C NMR (100M, CDCl 3 ), δ150.18, 142.90, 128.57, 124.36, 85.38 (d, J = 175.5Hz), 56.57, 49.46 (d, J = 28.3Hz), 42.22 ...

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Abstract

The invention relates to a method for synthesizing a fluoro nitrogen heterocyclic compound. In the method, a fluorine-containing hexahydropyridine compound is obtained with high selectivity through olefin fluoronation and amination which are performed in the presence of a metal catalyst by starting from simple nitrogen-containing olefins and using a hypervalent iodine compound as an oxidant and an inorganic fluoride as a fluorine source.

Description

technical field [0001] The invention relates to a method for synthesizing a fluorinated ammonia-containing heterocyclic compound, which is a method for preparing a fluorinated nitrogen-containing six-membered heterocyclic ring from an alkene. Background technique [0002] Nitrogen-containing heterocyclic rings are widely used in the fields of medicine, pesticides and materials. By introducing fluoride ions into medicines, pesticides and biomolecules, the activity and efficacy of drugs can be greatly improved. The introduction of fluorine atoms into the material molecules can greatly improve the performance of the material. For example, through SciFinder search, it is found that the drugs and their lead compounds described in a large number of patents contain fluorinated nitrogen-containing heterocycles. However, currently, such fluorinated nitrogen-containing heterocycles are synthesized through classical fluorination reactions, such as the fluorination of alcohols using DA...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B61/00C07B39/00C07D211/02C07D211/96C07D215/58C07D223/04
Inventor 刘国生吴涛
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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