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Benzo dioxy heterocyclic derivatives with optical activity and preparation method and application thereof

A benzodioxane and optically active technology, which is applied in the field of preparation of benzodioxane derivatives, can solve the problems of cumbersome synthesis methods and large operation risks, and achieve high yield, high selectivity, Compositing cheap effects

Inactive Publication Date: 2014-09-24
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above two synthesis methods are cumbersome, or the substituents are introduced through ozonation, which has greater operational risk.

Method used

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  • Benzo dioxy heterocyclic derivatives with optical activity and preparation method and application thereof
  • Benzo dioxy heterocyclic derivatives with optical activity and preparation method and application thereof
  • Benzo dioxy heterocyclic derivatives with optical activity and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Aromatic aldehyde 1:

[0042] Weigh aromatic aldehyde 1 (0.20mmol), rhodium acetate (1.00mg, 0.002mmol), chiral phosphoric acid A (8.6mg, 0.01mmol) p-bromoaniline (0.30mmol), Molecular sieves (100 mg) put them into a small test tube reactor, add redistilled 2.0 ml of dichloromethane, and stir at room temperature for 2 hours. Weigh phenyldiazoacetate methyl ester (0.30mmol) and dissolve it in 1.0ml redistilled methylene chloride, and inject it into the reaction system through a peristaltic pump for 1 hour, continue to stir for 2 hours after the injection, filter, and add 1 , 8-diazabicyclo[5.4.0]undec-7-ene (0.2mmol), stirred overnight at room temperature, and then passed column chromatography (eluent: petroleum ether: ethyl acetate=1:20~ 1:5) were isolated to obtain optically active benzodioxane derivatives

[0043]

[0044] 3.49(s, 3H), 3.10(qd, J=15.3, 4.4Hz, 2H).

[0045] 13 C NMR (101MHz, CDCl 3 )δ168.79,168.26,156.22,144.30,136.60,130.87,130.62,129.67,12...

Embodiment 2

[0047] Aromatic aldehyde 1:

[0048] Weigh aromatic aldehyde 1 (0.20mmol), rhodium acetate (1.00mg, 0.002mmol), chiral phosphoric acid B (5.0mg, 0.01mmol) p-bromoaniline (0.30mmol), Molecular sieves (100 mg) put them into a small test tube reactor, add redistilled 2.0 ml of dichloromethane, and stir at room temperature for 2 hours. Weigh phenyldiazoacetate methyl ester (0.30mmol) and dissolve it in 1.0ml redistilled methylene chloride, and inject it into the reaction system through a peristaltic pump for 1 hour, continue to stir for 2 hours after the injection, filter, and add 1 , 8-diazabicyclo[5.4.0]undec-7-ene (0.2mmol), stirred overnight at room temperature, and then passed column chromatography (eluent: petroleum ether: ethyl acetate=1:20~ 1:5) The optically active benzodioxane derivative 2A was isolated. The yield was 48%, the dr value was greater than 95:5, and the ee was 78%.

[0049]

Embodiment 3

[0051] Weigh aromatic aldehyde 1 (0.20mmol), rhodium acetate (0.002mmol), p-bromoaniline (0.30mmol), chiral phosphoric acid A (0.01mmol), Molecular sieves (100 mg) put them into a small test tube reactor, add redistilled 2.0 ml of dichloromethane, and stir at room temperature for 2 hours. Take by weighing p-methylphenyldiazoacetic acid methyl ester (0.30mmol) and dissolve in 1.0ml redistilled dichloromethane, and inject in the reaction system by peristaltic pump 1 hour, after injecting, continue to stir for 2 hours, filter, to Add 1,8-diazabicyclo[5.4.0]undec-7-ene (0.2mmol) to the filtrate, stir overnight at room temperature, then pass through column chromatography (eluent: petroleum ether: ethyl acetate=1 :20~1:5) The optically active benzodioxane derivative pure product 2B was isolated. The yield was 46%, the dr value was greater than 95:5, and the ee was 90%.

[0052]

[0053] 15.4, 5.5Hz, 2H).

[0054] 13 C NMR (101MHz, CDCl 3 )δ168.84,168.27,156.25,143.92,136.67...

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Abstract

The invention discloses benzo dioxy heterocyclic derivatives with optical activity and a preparation method and application thereof, and the products are synthesized by reaction of four components of a diazo compound, an ortho-substituted aromatic aldehyde, an arylamine and water under catalysis of rhodium acetate, chiral phosphoric acid and an alkali. The raw materials are cheap and easily obtained, three chiral carbons can be simultaneously constructed, the preparation route is short, the operation is simple and safe, the reaction condition is mild, the atom economy is high, the selectivity is high, and the polysubstituted benzo dioxy heterocyclic derivatives can be conveniently obtained, and diverse compound skeletons can be provided for use in screening of new drugs and pharmaceutical fields.

Description

technical field [0001] The invention belongs to the technical field of pharmaceutical synthesis chemistry and relates to a preparation method of optically active benzodioxane derivatives. Background technique [0002] Optically active dioxane derivatives are a class of important skeleton structures with special medicinal compounds. In the prior art, for example, Professor Peng Shiqi of Capital Medical University has proved through experiments that dioxo-heterocyclic compounds have good anti-inflammatory properties (Bioorg.Med.Chem.2006141339-1347), and its synthesis method is through multi-step natural amino acid prepared. Professor Roman S. Pavelyev from Russia proved that sulfur-containing dioxocyclic compounds have good antifungal activity (Mendeleev Commun., 2012, 22, 127-128), and the activity of optically active dioxocyclic compounds is better than that of racemates . However, the above two synthetic methods are cumbersome, or the substituents are introduced through...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D321/10C07D321/12A61P3/04A61P3/10
CPCC07D321/10C07D321/12
Inventor 胡文浩邱林郭鑫马超群刘顺英杨琍苹赵芸
Owner EAST CHINA NORMAL UNIV
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