Novel method for asymmetrically catalyzing (S)-arturmerone

A synthetic method, the technology of aromatic curcumone, applied in the field of new asymmetric catalytic synthesis-aromatic curcumone, can solve the problems of cumbersome reaction steps, harsh reaction conditions, a large number of chiral source reagents, etc. The effect of high purity

Active Publication Date: 2014-05-14
CHINA AGRI UNIV
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  • Abstract
  • Description
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Problems solved by technology

[0009] Although there have been some reports on the asymmetric synthesis of (S)-aromatic curcumone, there are some problems, such as the need for a large amount of chiral source reagents, harsh

Method used

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  • Novel method for asymmetrically catalyzing (S)-arturmerone
  • Novel method for asymmetrically catalyzing (S)-arturmerone
  • Novel method for asymmetrically catalyzing (S)-arturmerone

Examples

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Example Embodiment

[0021] Example 1

[0022] Synthesis of (R)-Benzyl p-Toluene Propionate 2

[0023] Add CoI to a dry Schlenk bottle under argon protection 2 (187.2mg, 0.6mmol), dried in vacuum for 2h, added anhydrous tetrahydrofuran (18mL) and bisoxazoline chiral ligand L1 (261.0mg, 0.72mmol), stirred at room temperature for 1h. Add racemic 2-bromophenylpropionate (1.45g, 6mmol) to the mixture, reduce the temperature of the reaction solution to -80℃, and add p-methylmagnesium bromide (12mL, 1.0M THF solution, 12mmol) dropwise ). The reaction was continued to be stirred at -80°C for 12h, and saturated aqueous ammonium chloride solution was added to quench the reaction. The reaction solution was extracted with ether, and the organic layers were combined, dried over anhydrous sodium sulfate, concentrated under reduced pressure and purified by silica gel column chromatography (n-hexane / ethyl acetate 40:1) to obtain a colorless oil (R)-p-toluenepropionic acid Benzyl ester 2 (1.34 g, yield 88%, optical...

Example Embodiment

[0026] Example 2

[0027] Synthesis of (R)-p-toluenepropanol 3

[0028] Under the protection of argon, a solution of (R)-benzyl p-toluenepropionate 2 (1.27g, 5mmol) in dichloromethane (60mL) was reduced to -78℃, and diisobutylaluminum hydride ( DIBAL-H) ​​(12mL, 1.0M toluene solution, 12mmol), warm up to room temperature and continue to stir the reaction until TLC monitors that there is no raw material. The reaction is quenched with potassium sodium tartrate aqueous solution (60mL), and stirring is continued for 6h. The organic phase was separated, and the aqueous phase was extracted with dichloromethane. The organic layers were combined, washed with water, dried over anhydrous sodium sulfate, concentrated under reduced pressure and purified by silica gel column chromatography (n-hexane / ethyl acetate 4:1) to obtain a colorless oil (R)-p-toluenepropanol 3 (0.71 g, yield 94%, optical purity 92%). [α] D 20 =+15.9(c1.1,CHCl 3 ); 1 H NMR(300MHz, CDCl 3 )δ: 7.16-7.10(m,4H), 3.65(d,J=6...

Example Embodiment

[0029] Example 3

[0030] Synthesis of (S)-p-toluene butyraldehyde 4

[0031] Under argon protection, dissolve (R)-p-toluenepropanol 3 (0.6g, 4mmol) in dichloromethane (16mL), add triethylamine (0.81g, 1.2mL, 8mmol) and p-toluenesulfonate at 0℃ Acid chloride (0.9g, 0.76mmol), after stirring the reaction for 6 hours, use NH 4 The reaction was quenched with Cl aqueous solution, the aqueous phase was extracted with diethyl ether, the organic phases were combined and washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the crude sulfonate of p-toluene propanol. The crude sulfonate was dissolved in DMSO (8 mL), NaCN (0.39 g, 8 mmol) was added, and the reaction was stirred at 50° C. for 1 h. The reaction solution was diluted with water, and the aqueous phase was extracted with dichloromethane. The organic layers were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product of p-...

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Abstract

The invention discloses a novel method for asymmetrically catalyzing (S)-ar-turmerone. The method comprises the following steps: by taking racemic 2-bromine propionic ester as an initial raw material, performing asymmetric Kumada cross coupling reaction under the catalysis of bioxazoline/cobalt to prepare para-toluene propionic ester, carrying out reduction and sulfonylation reaction to generate sulphonate of para-toluene propanol, subsequently carrying out cyaniding and reduction reaction to preparing para-toluene butyraldehyde, finally reacting with isocrotyl magnesium bromide, and oxidizing with PDC (Polycrystalline Diamond Compact) into the (S)-arturmerone. The method has a small amount of reaction steps, the total yield of the whole synthesis route is 31%, and the optical purity of a product is high (92%ee).

Description

technical field [0001] The invention relates to the field of chemical synthesis of natural products, in particular to a new method for asymmetric catalytic synthesis of (S)-aryl curcumone. Background technique [0002] (S)-aromatic curcuminoids mainly exist in the rhizomes of Zingiberaceae Curcuma longa plants, and have various physiological activities such as cytotoxicity, anti-inflammation, and anti-venom (Ji, M.; Choi, J.; Lee, J.; Lee , Y. Int. J. Mol. Med. 2004, 14(2), 253–256. Hong, C.H.; Noh, M.S.; Lee, W.Y.; Lee, S.K. Ferriera, L.A.; Henriques, O.B.; Andreoni, A.A.; Vital, G.R.; Campos, M.M.; Habermehl, G.G.; Moraes, V.L. Toxicon 1992, 30(10), 1211–1218.). The structural formula of (S)-aromatic curcumone is shown in formula 1, and there is a chiral methyl group in its structure. [0003] [0004] The limited content of (S)-ar-Turmerone in related plant resources and the high cost of extraction have prompted people to study its chemical synthesis. The key to the...

Claims

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Application Information

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IPC IPC(8): C07C49/217C07C45/29
CPCC07B53/00C07B2200/07C07C29/147C07C45/29C07C67/343C07C49/217C07C69/612C07C33/20
Inventor 钟江春边庆花毛建友刘飞鹏郑冰王敏武林杨燕青
Owner CHINA AGRI UNIV
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