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Urazole chiral axis compound and catalytic asymmetric synthesis method thereof

A synthetic method and axial chiral technology, which is applied in the field of ureazoline axial chiral compounds and their catalytic asymmetric synthesis, achieving the effects of easy preparation, good stability, and good enantioselectivity

Active Publication Date: 2016-02-17
SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] At present, there are other methods for synthesizing these compounds, but there is no report on the direct construction of chiral ureadiazoles by catalytic enantioselectivity

Method used

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  • Urazole chiral axis compound and catalytic asymmetric synthesis method thereof
  • Urazole chiral axis compound and catalytic asymmetric synthesis method thereof
  • Urazole chiral axis compound and catalytic asymmetric synthesis method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0058]

[0059] Dissolve 0.12 mmol of compound 2a and chiral catalyst C7 (5 mol%, 0.005 mmol) in 2 mL of ether in a Schlenk tube, stir the resulting solution at -78°C for 10 min, then add 0.10 mmol of compound 1a, and react for 30 min until the red color disappears After monitoring the reaction with TLC, the reaction solution was acidified with 6N hydrochloric acid, concentrated, and subjected to silica gel column chromatography (CH 2 Cl 2 ~CH 2 Cl 2 / Acetone=10 / 1) The product 3a was obtained after purification.

[0060] At room temperature, 0.2 mmol of compound 3a and 2.0 mmol of methyl iodide were dissolved in 1 mL of 1,4-dioxane, 0.4 mmol of potassium carbonate was added, and the resulting solution was stirred at room temperature for 5 h, and subjected to silica gel column chromatography (EA / PE=1: 2) The product 6a is obtained.

[0061] Compound 3a: 82% yield; 99% ee;

[0062] HPLC conditions: Daicel CHIRALPAKAD-H column, hexane (n-hexane) / i-PrOH=85 / 15, 0.8mL / min, T...

Embodiment 2

[0067] According to the method of Example 1, the solvent is ethylene dichloride, the catalyst consumption is 10 mmol%, the catalyst is C1, and the reaction is completed within 5 minutes. Compound 3a: 57% yield; 25% ee.

Embodiment 3

[0069] According to the method of Example 1, the solvent is ethylene dichloride, the catalyst consumption is 10 mmol%, the catalyst is C2, and the reaction is completed within 5 minutes. Compound 3a: 59% yield; 5% ee.

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Abstract

The invention discloses an urazole chiral axis compound. The urazole chiral axis compound is represented by a formula I or II, wherein the R<1a> is selected from alkyl, halogen, phenyl, substituted phenyl and other groups shown in the descriptions, the R<5> is selected from halogen, alkyl and alkoxy, the R<6> and the R<7> are respectively and independently selected from an aliphatic substituent group and an aromatic substituent group, and the R<1b>, R<1c>, R<1d> and R<1e> are respectively and independently selected from hydrogen, halogen, phenyl, substituted phenyl, alkyl, alkoxy, hydroxyl, a ester group, an aldehyde group, a cyano group and amide. The R represents an aryl group free of a substituent group or provided with one or more of substituent groups, and the R' represents hydrogen or alkyl. The invention further discloses an asymmetric synthesis method of the compound. The high-yield high-ee-value urazole chiral axis compound is prepared through synthesis under the moderate reaction conditions. The synthesis method has very good substrate adaptability and can achieve synthesis of more than shown grams of the compound under the situation that the dosage of a catalyst is decreased. The compound can serve as a catalyst or a ligand for a certain asymmetric reactions.

Description

technical field [0001] The invention relates to a class of ureazoline axial chiral compounds and a catalytic asymmetric synthesis method thereof. Background technique [0002] Urazole is an important heterocyclic compound. Due to its simple chemical synthesis and easy optimization of reaction conditions, urazole has potential application value in the fields of medicine and protein chemical modification. Furthermore, the oxidation of ureazoline can provide a class of persistent cyclic hydrazine radicals for multifunctional switching. Therefore, ureaazole compounds have broad application prospects. [0003] The click reaction of tyrosine provides a simple strategy to synthesize such compounds under mild conditions. Reaction of phenolic side chains to urazoles and use in bioconjugation chemistry. [0004] [0005] There are other methods for synthesizing these compounds, but there is no report on the direct construction of chiral ureadiazoles by catalytic enantioselectivi...

Claims

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Application Information

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IPC IPC(8): C07D249/12C07D403/04B01J31/02C07D209/38
CPCB01J31/0244B01J2231/34C07D209/38C07D249/12C07D403/04
Inventor 谭斌刘心元张纪伟许金辉程道娟
Owner SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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