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Method for catalyzing asymmetric Michael addition through alpha, beta-unsaturated ketone and sulfonyl compound and application thereof

A compound, unsaturated technology, applied in the field of chemistry, can solve the problem of low reactivity, achieve good selectivity, mild conditions, and a wide range of reaction substrates

Inactive Publication Date: 2011-02-16
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Bisphenylsulfonylmethane is an important methylating reagent. In 2009, Ramon Rios reported the reaction of bisphenylsulfonylmethane with enaldehyde and was used to synthesize Isotope-Enantiomers (Chem.Eur.J.2009, 15, 11095 ), but due to its relatively low reactivity, the asymmetric Michael addition reaction of bisbenzenesulfonylmethane and enone has been a difficult problem in organic catalysis. reaction, it is of great significance to provide a simple and effective methylation method

Method used

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  • Method for catalyzing asymmetric Michael addition through alpha, beta-unsaturated ketone and sulfonyl compound and application thereof
  • Method for catalyzing asymmetric Michael addition through alpha, beta-unsaturated ketone and sulfonyl compound and application thereof
  • Method for catalyzing asymmetric Michael addition through alpha, beta-unsaturated ketone and sulfonyl compound and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058] The reaction formula is:

[0059]

[0060] Add 0.2mL of dichloromethane to the reactor, then add bisphenylsulfonylmethane (44.4mg, 0.15mmol), 3-octen-2-one (12.6mg, 0.1mmol), benzoic acid (1.22mg, 0.02mmol ), catalyst 7-a (2.28mg, 0.02mmol), after feeding, the reactor was closed and stirred at 35°C for 48 hours; the reaction solution was concentrated under reduced pressure and separated by silica gel chromatography (petroleum ether / ethyl acetate =10:1), 36.3 mg of the addition product was obtained as a white solid, with a yield of 86%, a melting point of 78° C., and an optical rotation [α] 24 D =-10.3° (c=1.0, CH 2 Cl 2 ). 1 H NMR (400MHz, CDCl 3 ): δ (ppm) 7.92 (dd, J = 7.6, 20.4Hz, 4H), 7.69 (q, J = 7.2Hz, 2H), 7.57 (m, 4H), 4.82 (s, 1H), 3.12 (dd, J=4.0, 18.0Hz, 1H), 3.02~2.89(m, 2H), 2.10(s, 3H), 2.02~1.94(m, 1H), 1.61~1.52(m, 1H), 1.25~1.09(m, 4H), 0.85(t, .J=6.8Hz, 3H). 13 C NMR (100MHz, CDCl 3 ): δ (ppm) 206.9, 140.3, 138.3, 134.5, 134.3, 129.6, 129.1...

Embodiment 2

[0065] The reaction formula is:

[0066]

[0067] 0.5mL of 1,4-dioxane was added to the reactor, and then bisphenylsulfonylmethane (322mg, 0.75mmol), 3-penten-2-one (42mg, 0.5mmol), benzoic acid (24.4mg , 0.2mmol), catalyst 11-a (32.3mg, 0.1mmol), after feeding, the reactor was closed and stirred at 35°C for 48 hours; Separation (petroleum ether / ethyl acetate=10:1) gave 167.2 mg of the addition product as a white solid, with a yield of 88%, a melting point of 102-103° C., and an optical rotation [α] 20 D =+10.3 (c=0.7, CH 2 Cl 2 ). 1 H NMR (400MHz, CDCl3): δ(ppm) 7.91~7.89(m, 4H), 7.68(t, J=7.2, 2H), 7.57~7.52(m, 4H), 4.89(s, 1H), 3.20~ 3.10(m, 2H), 2.84(dd, J=6.4, 17.6Hz, 1H), 2.10(s, 3H), 1.40(d, J=6.8Hz, 3H). 13 C NMR (100MHz, CDCl3): δ (ppm) 207.1, 139.6, 139.1, 134.4, 134.3, 129.5, 129.1, 128.9, 84.9, 46.4, 30.2, 29.3, 18.1. HRMS (ESI): theoretical [M+NH 4 ] + (C 18 h 24 NO 5 S 2 ) is 398.1096, the actual m / z 398.1095. Chiral analysis was obtained by HPLC,...

Embodiment 3

[0069] The difference from Reaction Example 2 is: the α used, the β-unsaturated ketone is 3-hepten-2-one, and other experimental methods and conditions are the same as Reaction Example 2, and the addition product of white solid is obtained. The yield is 96%, melting point 113-116°C, optical rotation [α] 24 D =-12.0° (c=1.0, CH 2 Cl 2 ). 1 H NMR (400MHz, CDCl3): δ (ppm) 7.92 (dd, J=8.0, 20.4Hz, 4H), 7.69 (q, J=7.6Hz, 2H), 7.57 (qn, J=8.0Hz, 4H), 4.82(s, 1H), 3.12(dd, J=4.4Hz, 1H), 3.05~2.99(m, 1H), 2.92(dd, J=7.6Hz, 1H), 2.10(s, 1H), 2.01~1.92 (m, 1H), 1.61~1.52(m, 1H), 1.27~1.12(m, 2H), 0.84(t, J=7.6Hz, 3H); 13 C NMR (100MHz, CDCl3): δ (ppm) 206.9, 104.2, 138.3, 134.5, 134.3, 129.5, 129.1, 129.1, 128.7, 83.2, 44.1, 34.2, 33.6, 30.2, 20.7, 13.4. HRMS (ESI): theoretical Value [M+Na+H] + (C 20 h 25 NaO 5 S 2 ) is 432.1041, and the net result is 432.1039. Chiral analysis was obtained by HPLC, and the specific conditions were: [AS-H column, 220nm, n-Hexane:EtOH=7:3, 0.6...

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Abstract

The invention relates to a method for catalyzing asymmetric Michael addition through an alpha, beta-unsaturated ketone and sulfonyl compound and application thereof in the synthesis of apione. The alpha, beta-unsaturated ketone and sulfonyl compound is used as a raw material, a chiral catalyst respectively containing one or more than one primary amine, tertiary amine, urea or thiourea as a functional group or a salt thereof is used as a catalyst system, and an organic solvent is used as a reaction carrier. The reaction is carried out in a reaction kettle, the reaction temperature is 0-50 DEG C, the reaction temperature is 0-50 DEG C, the reaction time is 48-169 h, and the addition product is obtained. The general formula of the reaction is shown in the specification, wherein R1 and R2 are straight-chain or branched-chain alkyl substituent or aromatic substituent; and Nu is phenylsulfonyl, acetyl and aromatic compounds. The reaction of the alpha, beta-unsaturated ketone and sulfonyl compound is realized for the first time, and the invention has the advantages of high conversion rate, good selectivity, wide reaction substrate range, cheap and easily acquired reaction reagent and high yield reaching 97%; and chiral apione can be synthesized successfully.

Description

【Technical field】 [0001] The present invention relates to chemical technical field, relate to the chemical reaction process of asymmetric catalysis, specifically, be α, the method for the catalysis asymmetric Michael addition of β-unsaturated ketone and sulfone group (sulfonyl) compound and its application in the synthesis of celery Application in ketones. 【Background technique】 [0002] Sulfone-based compounds are an important class of functional groups in the field of organic synthesis. Due to their high reactivity and easy elimination of sulfone groups, they can easily introduce groups that are difficult to achieve by other methods, and are a good way to construct carbon-carbon bonds. In recent years, It has been favored by many chemists and widely used in asymmetric catalysis and organic synthesis. [0003] As an important nucleophile or electrophile, sulfone group has been widely used in metal catalysis and phase transfer catalysis. In 1995, Trost applied metal pallad...

Claims

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Application Information

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IPC IPC(8): C07C49/603C07C315/04C07C317/24C07C45/56
Inventor 叶金星孙小敏
Owner EAST CHINA UNIV OF SCI & TECH