Multifunctional chiral amine compound, preparation method and application thereof

A chiral amine, multifunctional technology, applied in the direction of sulfonamide preparation, chemical instruments and methods, organic compound/hydride/coordination complex catalyst, etc., can solve the problem of limited yield, low non-corresponding selectivity, cinchona The high price of alkaloids and other problems can achieve the effect of high-efficiency catalytic performance and strong synergy

Inactive Publication Date: 2014-05-07
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] For the application of chiral primary amines in asymmetrically catalyzed Michael addition reactions, although 9-amino(deoxy)quinine and 9-amino(deoxy)quinidine based on cinchona alkaloids are in many α, β- Good progress has been made in reactions such as Michael addition or epoxidation and aziridine of unsaturated ketones, but for many reactions, the non-enantioselectivity and enantioselectivity of this type of catalyst are low, such as α , The Michael addition reaction of β-unsaturated ketones and 2(5H)-furanone has very low non-corresponding selectivity, and 2(5H)-furanone is an important structural unit of many drug molecules and natural products
In addition, the expensive price and limited output of cinchona alkaloids are also factors restricting its application.

Method used

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  • Multifunctional chiral amine compound, preparation method and application thereof
  • Multifunctional chiral amine compound, preparation method and application thereof
  • Multifunctional chiral amine compound, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

preparation Embodiment 1

[0036]

[0037] (R,R)-1,2-Diphenylethylenediamine (4.24g, 20.0mmol) was dissolved in 40mL of anhydrous tetrahydrofuran, and triethylamine (2.7mL) was added in an ice-water bath. Under an ice-water bath, a solution of p-toluenesulfonyl chloride (3.82 g, 20.0 mmol) in 50 mL of anhydrous THF was slowly added dropwise to the above mixture. After the dropwise addition, the mixture was stirred at room temperature for 12 hours, and the solvent was removed from the mixture under reduced pressure. The residue was separated by silica gel column chromatography (petroleum ether: ethyl acetate = 1:1) to obtain 7.25 g of white solid with a yield of 90%.

[0038] The above product (2.16, 8.0mmol) was dissolved in 40mL of anhydrous acetonitrile, and 40ml of (S)-N-p-nitrobenzenesulfonyl-1-isopropyl-cycloethyleneimine (2.93, 8.0mmol) was added at room temperature The acetonitrile solution was stirred at 40°C for 12 hours, and the reaction was completed as detected by TLC. The mixture was con...

preparation Embodiment 2

[0044] The difference from Example 1 is that the N-protected ethyleneimine used is (S) N-p-nitrobenzenesulfonyl-1-benzyl-ethyleneimine, and other experimental methods and conditions are the same as in the examples 1, the final product is a white solid (product configuration is R, R, S; R 1 is benzyl, R 2 for hydrogen, R 3 is phenyl, R 4 is phenyl, R 5 is p-toluenesulfonyl), the structure is shown in the figure on the right.

[0045]

[0046] Melting point 164-165℃, optical rotation [α] 20 D -20.3 (c 1.0, CH 2 Cl 2 ); 1 H NMR (400MHz, CDCl 3 ): δ (ppm) 7.40-7.38 (m, 2H), 7.32-7.29 (m, 2H), 7.25-7.21 (m, 1H), 7.16-7.11 (m, 5H), 7.07-7.01 (m, 5H) , 6.96-6.93(m, 4H), 4.32(d, J=8.0Hz, 1H), 3.64(d, J=8.0Hz, 1H), 3.03-2.98(m, 1H), 2.72(dd, J=4.4 , 13.2Hz, 1H), 2.50(dd, J=4.0, 11.6Hz, 1H), 2.44-2.39(m, 1H), 2.34(s, 3H), 2.26-2.21(m, 1H). 13 CNMR (100MHz, CDCl 3 ): δ (ppm) 142.5, 139.6, 138.9, 138.6, 137.6, 129.2, 129.1, 128.5, 128.3, 127.8, 127.6, 127.5, 127.4, 127.1, ...

preparation Embodiment 3

[0048] The difference from Example 1 is that the N-protected ethyleneimine used is (S) N-p-nitrobenzenesulfonate

[0049]

[0050] Acyl-1-isobutyl-cycloethyleneimine, other experimental methods and conditions are the same as in Example 1, and the final product is a white solid (the product configuration is R, R, S; R 1 is isobutyl, R 2 is X hydrogen, R 3 is phenyl, R 4 is phenyl, R 5 is p-toluenesulfonyl), the structure is shown in the figure on the right.

[0051] Melting point 120-121℃, optical rotation [α] 20 D -39.3 (c 1.0, CH 2 Cl 2 ); 1 H NMR (400MHz, CDCl 3 ): δ (ppm) 7.41-7.39 (m, 2H), 7.16-7.15 (m, 3H), 7.06-7.03 (m, 5H), 6.96-6.94 (m, 4H), 4.33 (d, J=8.0Hz , 1H), 3.64(d, J=8.8Hz, 1H), 2.80-2.74(m, 1H), 2.45-2.41(m, 1H), 2.35(s, 3H), 2.15-2.10(m, 1H), 1.66-1.60(m, 1H), 1.13-1.09(m, 1H), 0.88(d, J=6.8Hz, 3H), 0.86(d, J=6.8Hz, 3H). 13 C NMR (100MHz, CDCl 3 ): δ (ppm) 142.7, 139.6, 138.4, 137.3, 129.1, 128.3, 127.9, 127.6, 127.5, 127.4, 127.2, 127.1, 68.5...

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Abstract

The invention relates to a multifunctional chiral amin compound, a preparation method and an application of the multifunctional chiral amine compound in an asymmetric Michael addition reaction of alpha, beta-unsaturated ketone and 2(5H)-furaneol. A general formula of the multifunctional chiral amine compound is shown in the description, wherein R1, R2, R3, and R4 are each differently or similarly selected from an alkane substituent or an aromatic substituent, R5 is selected from sulfuryl or sulfinyl or amide substituent. The multifunctional chiral amine compound and salts thereof provided by the present invention have wide applications, for example, the multifunctional chiral amine compound and the salts thereof can be adopted as chiral catalysts for the asymmetric Michael addition reaction. Especially that the chiral amine salt provided by the present invention provides high catalytic activity and high stereoselectivity for the asymmetric Michael addition reaction of the alpha, beta-unsaturated ketone and the 2(5H)-furaneol, wherein diastereoselectivity is up to 30 / 1, enantioselectivity is up to 99%, and reaction substrate scope is wide.

Description

【Technical field】 [0001] The invention relates to a chiral amine compound and a preparation method thereof, and the application of the compound or its salt as a catalyst in the asymmetric Michael addition reaction of α, β-unsaturated ketones and 2(5H)-furanone . 【Background technique】 [0002] Chiral amines are the structural units of many drug molecules, bioactive molecules and natural products, and are also ligands for many asymmetric catalytic reactions. Therefore, the development of new chiral amines has always been the goal pursued by chemists. In recent years, chiral tertiary amines (Chem.Rev., 2003, 103, 2985, Acc.Chem.Res., 2004, 37, 621, Acc.Chem.Res., 2004, 37, 542), chiral secondary Amines (Chem. Rev., 2007, 107, 5416, Chem. Rev., 2007, 107, 5471) and chiral primary amines (Chem. Commun., 2009, 1807) are good organic catalysts. Amine-catalyzed reactions include reactions catalyzed by tertiary, secondary, and primary amines, and tertiary and secondary amines are ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C311/18C07C303/40C07C303/38B01J31/02C07D307/58C07D409/06
Inventor 叶金星梁鑫淼黄慧才周宇峰于峰金智超
Owner EAST CHINA UNIV OF SCI & TECH
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