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Novel method for synthesizing chiral 4-nitryl-3, 5-diaryl cyclohexanone

A cyclohexanone and chiral technology, applied in the field of asymmetric catalysis, can solve the problems of expensive raw materials and difficult to obtain prices, and achieve the effects of high yield, excellent diastereoselectivity and good enantioselectivity

Inactive Publication Date: 2011-08-17
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] But the raw material that above-mentioned technical scheme involves is difficult to obtain and expensive

Method used

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  • Novel method for synthesizing chiral 4-nitryl-3, 5-diaryl cyclohexanone
  • Novel method for synthesizing chiral 4-nitryl-3, 5-diaryl cyclohexanone
  • Novel method for synthesizing chiral 4-nitryl-3, 5-diaryl cyclohexanone

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039]

[0040] 1a (58.5 mg, 0.25 mmol), nitromethane (263.2 uL, 5.0 mmol) and thiourea catalyst (29.7 mg, 0.05 mmol) were successively charged into the reaction flask, and 1 mL of toluene was added, and the reaction was carried out at room temperature for 24-72 hours. After column chromatography (eluent: ethyl acetate:petroleum ether=1:5-1:10) to separate the starting material and catalyst, the residue was dissolved in potassium hydroxide (1.1 mg, 0.020 mmol) in ethanol (2 mL) In, react at 0 DEG C for 2 hours, obtain crude product;

[0041] The reaction system was quenched with saturated ammonium chloride, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The crude product was subjected to simple column chromatography (eluent: ethyl acetate:petroleum ether=1:10 ) to obtain the target product 3a (63.5 mg) with a yield of 86%.

[0042] The product is analyzed and the results are as follows: 1 H NMR (400 MH...

Embodiment 2

[0044]

[0045] 1a (58.5 mg, 0.25 mmol), nitromethane (263.2 uL, 5.0 mmol) and thiourea catalyst (29.7 mg, 0.05 mmol) were successively charged into the reaction flask, and 1 mL of toluene was added, and the reaction was carried out at room temperature for 24-72 hours. After column chromatography (eluent: ethyl acetate:petroleum ether=1:5-1:10) to separate the starting material and catalyst, the residue was dissolved in potassium hydroxide (1.1 mg, 0.020 mmol) in ethanol (2 mL) In, react at 0 DEG C for 2 hours, obtain crude product;

[0046] The reaction system was quenched with saturated ammonium chloride, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The crude product was subjected to simple column chromatography (eluent: ethyl acetate:petroleum ether=1:10 ) to obtain the target product 3a' (28.1 mg), with a yield of 38%.

[0047] The product is analyzed and the results are as follows: 1 H NMR (400 ...

Embodiment 3

[0049]

[0050] 1b (88.5 mg, 0.25 mmol), nitromethane (263.2 uL, 5.0 mmol) and thiourea catalyst (29.7 mg, 0.05 mmol) were successively charged into the reaction flask, and 1 mL of toluene was added, and the reaction was carried out at room temperature for 24-72 hours. After column chromatography (eluent: ethyl acetate:petroleum ether=1:5-1:10) to separate the starting material and catalyst, the residue was dissolved in potassium hydroxide (1.1 mg, 0.020 mmol) in ethanol (2 mL) In, react at 0 DEG C for 2 hours, obtain crude product;

[0051] The reaction system was quenched with saturated ammonium chloride, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed. The crude product was subjected to simple column chromatography (eluent: ethyl acetate:petroleum ether=1:10 ) to obtain the target product 3b (79.8 mg), with a yield of 77%.

[0052] The product is analyzed and the results are as follows: 1 H NMR (300 M...

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Abstract

The invention belongs to the field of asymmetric synthesis, and particularly relates to a novel method for catalyzing and synthesizing a chiral 4-nitryl-3, 5-diaryl cyclohexanone compound by chiral thiocarbamide as a catalyst. The method comprises the following steps of: (1) reacting by taking diketene and nitromethane as a reaction substrate, quinine-derived thiocarbamide as a chiral catalyst and methylbenzene as solvent at the temperature of between 20 and 25 DEG C for 24 to 72 hours to generate a Michael addition product; and (2) reacting by taking the Michael addition product obtained in the step (1) as a reactant, potassium hydroxide as a catalyst and ethanol as solvent at the temperature of between 0 and 10 DEG C for 0.5 to 2 hours to obtain a chiral 4-nitryl-3, 5-diaryl cyclohexanone derivative. The novel method for synthesizing the chiral 4-nitryl-3, 5-diaryl cyclohexanone compound has the advantages of readily available materials and mild reaction conditions and is easy and convenient to operate, and a reaction system is insensitive to air, aqueous vapor and the like and aftertreatment is convenient, so the chiral 4-nitryl-3, 5-diaryl cyclohexanone compound is suitable for industrial production. Simultaneously, the synthetic method has the characteristics of high yield and excellent diastereoselectivity and enantioselectivity.

Description

technical field [0001] The invention belongs to the field of asymmetric catalysis, and in particular relates to a method for catalytically preparing chiral 4-nitro-3,5-diarylcyclohexanone compounds by using chiral thiourea as a catalyst. Background technique [0002] Functionalized chiral cyclohexanone derivatives are a class of biologically and physiologically active compounds, which are quite important in the synthesis of many natural products. Through literature research, we found that the molecular structures of many natural products and drugs contain fragments of chiral cyclohexanone derivatives, (see: [T. Bui, C. F. Barbas III, Tetrahedron Lett ., 2000, 41, 6951], [J. Jiang, J. L. Bunda, G. A. Doss, G. G. Chicchi, M.M. Kurtz, K. L. Tsao, C. X. Tong, S. Zheng, A. Upthagrove, K. Samuel, K. Tschirret-Guth, R. Kumar, S. Wheeldon, A. Carlson, E. J. Hargreaves, R. Burns, D. Hamill, T. Ryan, C. Krause, S. M. Eng, W. DeVita, R. J. Mills, S. G. J. Med. Chem ., 2009, 52, 3039...

Claims

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Application Information

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IPC IPC(8): C07C205/45C07C201/12C07D307/46C07D333/22
Inventor 王兴旺吴斌
Owner SUZHOU UNIV
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