Chiral arylallyl ether compound and synthesis method therefor

An aryl allyl ether and a synthesis method technology are applied in the fields of asymmetric nucleophilic SN2' substitution reaction, synthesis of chiral ether compounds, and efficient synthesis of chiral aryl allyl ether compounds, which can solve the problem of problems such as low optical purity, to achieve the effect of high optical purity, low cost and easy operation

Inactive Publication Date: 2017-10-20
CHANGZHOU UNIV
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  • Abstract
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AI Technical Summary

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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  • Chiral arylallyl ether compound and synthesis method therefor
  • Chiral arylallyl ether compound and synthesis method therefor
  • Chiral arylallyl ether compound and synthesis method therefor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] At room temperature, 18.8 mg of phenol and 175 mg of MBH adducts with tert-butoxyacyloxy were dissolved in 4 mL of 1,4-dioxane, and 32.8 mg of hydroquinidine 1,4-(2,3- Naphthalene) diether, stirred at room temperature for 96h, the solvent was removed, and the residue was separated by column chromatography to obtain compound 1a, whose molecular structural formula was: It is a colorless oil, 95% yield, 95%ee[determined by high performance liquid chromatography, chiral OD-H column, n-hexane:isopropanol=95:5, 0.5mL / min, 270nm, tR( minor)=11.1min, tR(major)=13.5min]. 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

[0034] At room temperature, 24.8 mg of p-methoxyphenol and 175 mg of MBH adducts with tert-butoxyacyloxy were dissolved in 4 mL of 1,4-dioxane, and 32.8 mg of hydroquinidine 1,4-(2 , 3-Naphthyridine) diether, stirred at room temperature for 89h, the solvent was removed, and the residue was separated by column chromatography to obtain compound 1b, whose molecular structural formula was: It is a colorless oil, 93% yield, 91%ee [determined by high performance liquid chromatography, chiral OD-H column, n-hexane:isopropanol=95:5, 0.5mL / min, 270nm, t R(minor) =11.2min,t R(major) = 10.1 min]. 1 H NMR (400MHz, CDCl 3 ):7.46-7.42(m,2H),7.37-7.25(m,3H),7.02(d,J=8.1Hz,2H),6.82(dd,J=2.1,6.6Hz,2H),6.38(s, 1H), 6.11(s, 1H), 5.97(t, J=1.1Hz, 1H), 3.74(s, 3H); 13 C NMR (100MHz, CDCl 3 ):166.2,155.5,140.3,139.0,130.5,129.9,128.5,128.1,127.5,126.3,115.8,77.4,52.0,20.5ppm.HRMS(ESI):C 18 h 18 NaO 3 [M+Na] + The theoretical value is 305.1148, and the measured value is 305.1149.

Embodiment 3

[0036] At room temperature, 25.7 mg of p-chlorophenol and 175 mg of MBH adducts with tert-butoxyacyloxy were dissolved in 4 mL of 1,4-dioxane, and 32.8 mg of hydroquinidine 1,4-(2 , 3-Naphthyridine) diether, stirred at room temperature for 96h, the solvent was removed, and the residue was separated by column chromatography to obtain compound 1c, whose molecular structural formula was: It is a colorless oil, 73% yield, 94%ee[determined by high performance liquid chromatography, chiral OD-H column, n-hexane:isopropanol=95:5, 0.5mL / min, 270nm, tR( minor)=12.2min, tR(major)=10.4min]. 1H NMR (400MHz, CDCl3): 7.44-7.41(m, 2H), 7.38-7.29(m, 3H), 7.17(d, J=9.0Hz, 2H), 6.84(d, J=9.3Hz, 2H), 6.39(s,1H),6.10(s,1H),5.92(t,J=1.1Hz,1H),3.75(s,3H);13C NMR(100MHz,CDCl3):166.0,156.1,139.9,138.3,129.3 , 128.6, 128.3, 127.3, 126.4, 126.1, 117.2, 77.6, 52.1ppm. HRMS (ESI): C17H15ClNaO3 [M+Na] + theoretical value 325.0602, measured value 325.0591.

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Abstract

The invention discloses a chiral arylallyl ether compound and a synthesis method therefor and belongs to the technical field of preparation of chemical pharmaceuticals and fine chemical industry. The compound is an important synthesis intermediate and has extensive bioactivity. According to the synthesis method, a series of arylallyl ether compounds with high optical purity are synthesized in a high-yield manner through subjecting cheap and readily-accessible aryl phenol compounds to a nucleophilic SN2' substitution reaction with an MBH reaction adduct with a leaving group in the presence of a chiral tertiary amine catalyst. The synthesis method provides a simple and practical technical route for the preparation of chiral arylallyl ether compounds and has extensive application in the technical field of preparation of chemical pharmaceuticals and fine chemical industry.

Description

technical field [0001] The invention relates to the synthesis of chiral ether compounds, that is, the efficient synthesis of chiral aryl allyl ether compounds. It mainly involves the asymmetric nucleophilic SN2' substitution reaction of MBH adducts with leaving groups by nucleophiles under organocatalysis. The invention provides an efficient, concise and practical route for the synthesis of chiral aryl allyl ether compounds. It 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. In addition, it also has a wide range of biological activities, and some derivatives have been proved t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/734C07C67/31
CPCC07B2200/07C07C67/31C07C69/734
Inventor 赵帅陈新金雷陈至立
Owner CHANGZHOU UNIV
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