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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[0012] But the raw material that above-mentioned techni...

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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.

Application Domain

Organic chemistryOrganic compound preparation

Technology Topic

SolventPotassium hydroxide +10

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Experimental program(16)

Example Embodiment

[0038] Example one:

[0039]

[0040] Fill the reaction flask with 1a (58.5 mg, 0.25 mmol), nitromethane (263.2 uL, 5.0 mmol) and thiourea catalyst (29.7 mg, 0.05 mmol), add 1mL of toluene, and react at room temperature for 24-72 hours. Column chromatography (eluent: ethyl acetate: petroleum ether=1:5-1:10) After separating the raw materials and the catalyst, the residue is dissolved in potassium hydroxide (1.1 mg, 0.020 mmol) in ethanol (2 mL) In, react at 0°C for 2 hours to obtain a crude product;

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

[0042] The product is analyzed, and the results are as follows: 1 H NMR (400 MHz, CDCl 3 ): δ 7.34 – 7.27 (m, 2H), 7.27 – 7.22 (m, 3H), 7.23 – 7.15 (m, 3H), 6.98 (dd, J = 13.7, 8.6 Hz, 2H), 5.22 (dd, J = 6.9, 4.8 Hz, 1H), 3.87 (dd, J = 14.0, 7.1 Hz, 1H), 3.81 – 3.61 (m, 1H), 3.26 (dd, J = 15.8, 9.4 Hz, 1H), 3.00 (dd, J = 16.2, 6.4 Hz, 1H), 2.93 – 2.67 (m, 2H). 13 C NMR (100MHz, CDCl 3 ):δ 42.0, 42.4, 42.6, 43.5, 91.7, 127.4, 127.8, 128.3, 128.6, 129.2, 129.5, 137.0, 139.6, 207.9 ppm. HRMS: calcd.for C 18 H 13 NO 3 295.1208, found: 295.1207. [α] rt D = +44.6(c =0.50, CHCl 3 , 90.2% ee), the above data proves that the target product was successfully prepared.

Example Embodiment

[0043] Embodiment two:

[0044]

[0045] Fill the reaction flask with 1a (58.5 mg, 0.25 mmol), nitromethane (263.2 uL, 5.0 mmol) and thiourea catalyst (29.7 mg, 0.05 mmol), add 1mL of toluene, and react at room temperature for 24-72 hours. Column chromatography (eluent: ethyl acetate: petroleum ether=1:5-1:10) After separating the raw materials and the catalyst, the residue is dissolved in potassium hydroxide (1.1 mg, 0.020 mmol) in ethanol (2 mL) In, react at 0°C for 2 hours to obtain a crude product;

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

[0047] The product is analyzed, and the results are as follows: 1 H NMR (400 MHz, CDCl 3 ): δ 7.34 – 7.27 (m, 2H), 7.27 – 7.22 (m, 3H), 7.23 – 7.15 (m, 3H), 6.98 (dd, J = 13.7, 8.6 Hz, 2H), 5.22 (dd, J = 6.9, 4.8 Hz, 1H), 3.87 (dd, J = 14.0, 7.1 Hz, 1H), 3.81 – 3.61 (m, 1H), 3.26 (dd, J = 15.8, 9.4 Hz, 1H), 3.00 (dd, J = 16.2, 6.4 Hz, 1H), 2.93 – 2.67 (m, 2H). 13 C NMR (100MHz, CDCl 3 ):δ 42.0, 42.4, 42.6, 43.5, 91.7, 127.4, 127.8, 128.3, 128.6, 129.2, 129.5, 137.0, 139.6, 207.9 ppm. HRMS: calcd.for C 18 H 13 NO 3 295.1208, found: 295.1210. [α] rt D = -45.8 (c =0.50, CHCl 3 , 93.2% ee), the above data proves that the target product was successfully prepared.

Example Embodiment

[0048] Embodiment three:

[0049]

[0050] Fill the reaction flask with 1b (88.5 mg, 0.25 mmol), nitromethane (263.2 uL, 5.0 mmol) and thiourea catalyst (29.7 mg, 0.05 mmol), add 1mL of toluene, and react at room temperature for 24-72 hours. Column chromatography (eluent: ethyl acetate: petroleum ether=1:5-1:10) After separating the raw materials and the catalyst, the residue is dissolved in potassium hydroxide (1.1 mg, 0.020 mmol) in ethanol (2 mL) In, react at 0°C for 2 hours to obtain a crude product;

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

[0052] The product is analyzed, and the results are as follows: 1 H NMR (300 MHz, CDCl 3 ): δ 6.37 (s, 3H), 6.20 (d, J = 1.8 Hz, 3H), 5.27 (dd, J = 6.8, 5.1 Hz, 1H), 4.12 (d, J = 7.1 Hz, 1H), 3.98 – 3.80 (m, 1H), 3.75 (d, J = 7.2 Hz, 12H), 3.25 (dd, J = 16.1, 9.3 Hz, 1H), 3.01 (dd, J = 16.3, 5.9 Hz,1H), 2.80 (dd, J = 15.4, 5.9 Hz, 2H). 13 C NMR (75MHz, CDCl 3 ):δ 42.0, 42.5, 42.9, 43.4, 55.5, 91.4, 99.6, 99.7, 139.3, 142.0, 161.2, 161.6, 207.8 ppm. HRMS: calcd.for C 18 H 13 NO 3 415.1631, found: 415.1633.[α] rt D = +26.3(c =1.00, CHCl 3 , 92.0% ee). The above data proves that the target product was successfully prepared.

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Simple ingredients
Raw materials are easy to get

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

AI-Extracted Technical Summary

Problems solved by technology

Abstract

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Examples

Example Embodiment

Example Embodiment

Example Embodiment

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Description & Claims & Application Information

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