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Method for organocatalytic synthesis of chiral aryl allyl ether compounds

An aryl allyl ether and compound technology, which is applied in the fields of chemical pharmacy and fine chemical preparation, can solve problems such as low optical purity, and achieve the effects of high optical purity, low cost and easy operation.

Active Publication Date: 2018-01-19
CHANGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] (2) Use chiral tertiary amines to catalyze the synthesis of chiral aryl allyl ether compounds, but the optical purity is very low
[0007] The above methods can only obtain racemic or aryl allyl ether compounds with very low optical purity, which has strong limitations

Method used

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  • Method for organocatalytic synthesis of chiral aryl allyl ether compounds
  • Method for organocatalytic synthesis of chiral aryl allyl ether compounds
  • Method for organocatalytic synthesis of chiral aryl allyl ether compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] At room temperature, dissolve 62.4 mg of MBH phenyl carbonate in 4 mL of tetrahydrofuran, add 32.8 mg of hydroquinidine 1,4-(2,3-naphthyridine) diether, stir at room temperature for 67 hours, and remove the solvent. The residue was separated by column chromatography to obtain compound 2a, whose molecular structural formula is: It is a colorless oil, 95% yield, 90%ee[determined by high performance liquid chromatography, chiral OD-H column, n-hexane:isopropanol=95:5, 0.5mL / min, 270nm, tR( minor)=12.3min, tR(major)=15.0min]. 1H NMR (400MHz, CDCl3): 7.46(d, J=1.8Hz, 2H), 7.44-7.20(m, 5H), 6.94-6.89(m, 3H), 6.39(s, 1H), 6.16(s, 1H ), 5.97(t, J=1.2Hz, 1H), 3.74(s, 3H); 13C NMR(100MHz, CDCl3): 166.0, 157.5, 140.1, 138.8, 129.4, 128.5, 128.1, 127.4, 126.3, 121.2, 115.9 , 77.2, 52.0ppm. HRMS (ESI): C17H16NaO3 [M+Na] + theoretical value 291.0992, measured value 291.0992.

Embodiment 2

[0031] At room temperature, dissolve 65.3 mg of o-methyl substituted MBH phenyl carbonate in 4 mL of tetrahydrofuran, add 32.8 mg of hydroquinidine 1,4-(2,3-naphthyridine) diether, and stir at room temperature for 66 hour, the solvent was removed, and the residue was separated by column chromatography to obtain compound 2b, whose molecular structural formula was: It is a colorless oil, 86% yield, 92%ee[determined by high performance liquid chromatography, chiral OD-H column, n-hexane:isopropanol=95:5, 0.5mL / min, 270nm, tR( minor)=16.5min, tR(major)=18.2min]. 1H NMR(400MHz, CDCl3):7.41-7.37(m,1H),7.25-7.19(m,5H),6.94-6.88(m,3H),6.44(s,1H),6.34(s,1H),5.74 (t,J=1.2Hz,1H),3.75(s,3H),2.36(s,3H);13C NMR(100MHz,CDCl3):166.3,157.9,139.1,136.3,136.2,130.6,129.4,128.2,127.6 , 127.1, 126.2, 121.1, 115.6, 74.5, 52.1, 19.2ppm. HRMS (ESI): C18H18NaO3 [M+Na] + theoretical value 305.1148, measured value 305.1151.

Embodiment 3

[0033] At room temperature, dissolve 65.3 mg of m-methyl-substituted MBH phenyl carbonate in 4 mL of tetrahydrofuran, add 32.8 mg of hydroquinidine 1,4-(2,3-naphthyridine) diether, and stir at room temperature for 66 hour, the solvent was removed, and the residue was separated by column chromatography to obtain compound 2c, whose molecular structural formula was: It is a colorless oil, 97% yield, 89%ee[determined by high performance liquid chromatography, chiral OD-H column, n-hexane:isopropanol=95:5, 0.5mL / min, 270nm, tR( minor)=9.1min, tR(major)=12.3min]. 1H NMR (400MHz, CDCl3): 7.25-7.20(m, 5H), 7.12-7.09(m, 1H), 6.94-6.89(m, 3H), 6.38(t, J=0.8Hz, 1H), 6.12(s ,1H),5.96(t,J=1.2Hz,1H),3.74(s,3H),2.34(s,3H);13C NMR(100MHz,CDCl3):166.1,157.6,140.0,138.7,138.2,129.3, 129.0,128.4,128.0,126.3,124.5,121.1,115.8,77.2,52.0,21.4ppm.HRMS(ESI):C18H18NaO3[M+Na] + The theoretical value is 305.1148, and the measured value is 305.1152.

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Abstract

Belonging to the technical field of chemical pharmacy and fine chemical preparation, the invention discloses a method for organocatalytic synthesis of chiral aryl allyl ether compounds. The compoundsare an important synthetic intermediate, and have wide biological activity in itself. Cheap and easily available raw materials are subjected to two-step synthesis reaction to obtain MBH phenyl carbonate, under the action of a tertiary amine catalyst, monomolecular CO2 is removed, and a series of chiral aryl allyl ether compounds can be synthesized with high yield and high selectivity. The invention provides a simple and practical technical route for preparation of chiral aryl allyl ether compounds, and the technical route has wide application in the technical field of chemical pharmacy and fine chemical preparation.

Description

technical field [0001] The present invention relates to the synthesis of chiral ether compounds, that is, the efficient synthesis of chiral aryl allyl ether compounds, mainly related to the deCO of MBH phenyl carbonate under organic catalysis 2 decomposition reaction. The invention provides an efficient and concise route for the synthesis of chiral aryl allyl ether compounds, has broad application prospects in the fields of chemical pharmacy and fine chemical industry, and belongs to the technical field of chemical pharmacy and fine chemical preparation. Background technique [0002] Chiral aryl allyl ether compounds are highly functionalized molecules, which are an important class of intermediates in organic synthesis. Many natural products and bioactive molecules can be synthesized through subsequent transformations. It also has a wide range of biological activities, and some derivatives have been proven to have good antibacterial activity. In the current literature, chi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/31C07C69/736
Inventor 赵帅陈新金雷陈至立
Owner CHANGZHOU UNIV