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Application of dehydroabietylamine thiourea catalyst in synthesizing chiral compound with high-antipodism both-hand control

A dehydroabietic amine and thiourea catalyst technology, which is applied in the preparation of organic compounds, asymmetric synthesis, organic compound/hydride/coordination complex catalysts, etc., can solve the unreported γ-nitro-aromatic heteroketone The synthesis method of chiral compounds, poor adaptability of cyclohexanediamine, low enantioselectivity, etc., achieve the effects of easy modification and preparation, low price, easy separation and recovery

Inactive Publication Date: 2008-12-10
LANZHOU UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the sugar ring moiety in the thiourea catalyst showed poor compatibility to (1S,2S)-cyclohexanediamine, resulting in the addition product (R) -γ-Nitroacetophenone not only showed poor yield but also relatively low enantioselectivity
More importantly, no related synthetic method for the synthesis of γ-nitro-aromatic heteroketone chiral compounds with high enantiomers has been reported so far.

Method used

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  • Application of dehydroabietylamine thiourea catalyst in synthesizing chiral compound with high-antipodism both-hand control
  • Application of dehydroabietylamine thiourea catalyst in synthesizing chiral compound with high-antipodism both-hand control
  • Application of dehydroabietylamine thiourea catalyst in synthesizing chiral compound with high-antipodism both-hand control

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Experimental program
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Effect test

Embodiment 1

[0046] Embodiment 1: dehydroabietamine-thiourea catalyst (abbreviation: (1R, 2R)-CHDA-DHATU), [English full name 1-((1R, 2R)-2-aminocyclohexyl)-3-(((1R, 4aS, 10aR)-7-isopropyl-1, 4a-dimethyl-1, 2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl)methyl)thiourea] structural formula is as follows:

[0047]

[0048] Dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU preparation method:

[0049] Dissolve 2.85g (10mmol) of dehydroabietamine in 50ml of anhydrous ether solution, and add 2.06g (10mmol) of dicyclohexylcarbodiimide (DCC). After stirring for 15 minutes, 4 ml (50 mmol) of carbon disulfide was added dropwise at 0° C., and the reaction was carried out at room temperature for 8 hours. After filtration and concentration of the filtrate, column chromatography (H60 silica gel, n-hexane:ethyl acetate=5:1) gave 3.1 g of isothiocyanate (95% yield).

[0050] Dissolve 1.14g (10mmol) (1R, 2R)-cyclohexanediamine in 40ml of anhydrous dichloromethane, and mix 3.1g of isothiocyanate di...

Embodiment 2

[0057] Embodiment 2: dehydroabietamine-thiourea catalyst (abbreviation: (1S, 2S)-CHDA-DHATU), [English full name: 1-((1S, 2S)-2-aminocyclohexyl)-3-(((1R , 4aS, 10aR)-7-isopropyl-1, 4a-dimethyl-1, 2,3,4,4a,9,10,10a-octahydrophenanthren-1-y1)methyl)thiourea] structural formula is as follows:

[0058]

[0059] The preparation method of dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU is the same as that of Example 1.

[0060] [α] 20 D =-57 (c=1.1, CHCl 3 ); melting point: 87-88C.

[0061] NMR analysis:

[0062] 1 H NMR (300MHz, [D 6 ]DMSO): δ7.40 (br, 1H), 7.14-7.16 (d, J=8.1Hz, 1H), 6.93-6.96 (dd, J=1.5Hz, 8.1Hz, 1H), 6.84 (s, 1H) , 3.75(br, 1H), 3.35-3.44(m, 2H), 2.71-2.78(m, 3H), 2.40-2.46(m, 1H), 2.24-2.28(d, J=12.9Hz, 1H), 2.00 (m, 1H), 1.47-1.87(m, 7H), 1.35-1.40(m, 2H), 1.21-1.25(m, 2H), 1.13-1.16(m, 9H), 0.95-0.96(m, 7H) ; 13 C NMR (75MHz, [D 6 ]DMSO): δ147.0, 144.9, 134.4, 126.4, 124.0, 123.5, 54.2, 44.5, 38.0, 37.4, 37.0, 34.2, 32.8, 31.5, 29.7, 25....

Embodiment 3

[0066] Example 3: (S)-4-nitro-1,3-diphenyl-1-butanone and (R)-4-nitro-1,3-diphenyl-1-butanone have the following structural formulas:

[0067]

[0068] a. The method for preparing (S)-4-nitro-1,3-diphenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU:

[0069] Dissolve 15mg (0.1mmol) substrate nitrostyrene, 6.6mg (0.015mmol) dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, 1.8mg (0.015mmol) benzoic acid in 0.8ml di In methyl chloride, 35 μl (0.3 mmol) of acetophenone was added at 0° C., and after 2 hours of reaction, the reaction was continued at room temperature for 60 hours. After the reaction was complete, it was extracted three times with dichloromethane (8ml each time), and dried with 2g of anhydrous sodium sulfate. Concentration and column chromatography (H60 silica gel, petroleum ether: ethyl acetate = 8: 1) gave the final product (S)-4-nitro-1,3-diphenyl-1-butanone 26.6 mg (99 %Yield).

[0070] [α] 20 D =-22 (c=1.0, CHCl 3 ); ...

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Abstract

The invention discloses an application of a dehydroabietylamine-chiral thiourea catalyst in both-hands synthesizing gamma-nitro-aromatic ketones and gamma-nitro-aromatic mixed ketones chiral compounds in a high enantiomer. The invention successfully utilizes the chiral source of the nature to synthesize a noveldehydroabietylamine-chiral thiourea catalyst with high catalytic activity. The catalyst has low price, is easy to decorate and prepare, is simple in treatment, can be separated or recycled from the products, can be reutilized and extends the limited range of known thiourea catalyst. The invention realizes that the same catalyst in the same reaction system can generate high optical pure target product with different configurations by high-efficiency and high-activity asymmetric catalysis. The method has simple operation, uses no metal reagent and has less environmental pollution. The reaction condition is mild and the reaction can be carried out in air rather than the strict anhydrous and oxygen-free conditions.

Description

technical field [0001] The invention relates to the application of a class of dehydroabietic amine-chiral thiourea catalysts in the dual-handed synthesis of gamma-nitro-aromatic ketones and gamma-nitro-aromatic heteroketone chiral compounds with high enantiomers. Background technique [0002] As a new concept in the 21st century, asymmetric organocatalysis has become an important tool for building molecular skeletons due to its high efficiency and high selectivity. It plays a huge role in organic synthesis and the pharmaceutical industry. The development of biology provides broad application prospects. Asymmetric Michael addition products: γ-nitrocarbonyl compounds are a class of very useful synthetic intermediates in organic synthesis. For example: gamma-nitro-aromatic ketones and gamma-nitro-aromatic heteroketone chiral compounds can be further converted into very useful chiral pyrrolidine derivatives etc. (R.Galeazzi, G.Martelli, G. Mobbili, M. Orena, S. Rinaldi, Tetrah...

Claims

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Application Information

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IPC IPC(8): B01J31/02C07C335/14C07C205/45C07C201/12C07D307/46C07D333/22C07D275/02C07B53/00
Inventor 王锐蒋先兴张义福
Owner LANZHOU UNIVERSITY
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