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Chiral amino sulfamide ligand metal complexes and applications in catalytic reactions

A technology of aminosulfonamide and sulfonimide, which is applied to chiral aminosulfonamide ligand metal complex and its application in catalytic reaction, can solve the problem that the product does not have chirality, the substrate universality is poor, etc. question

Active Publication Date: 2019-04-23
CHONGQING MEDICAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] In the reaction system of Fan Renhua et al., the direct Mannich reaction of the benzenesulfonyl-protected amino group was achieved, but the substrate universality was poor, and only the sulfonimide reaction of benzaldehyde was made, while other aldimines were not. Not very good results, more importantly, the product of this reaction is only a pure racemate, the product does not have chirality

Method used

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  • Chiral amino sulfamide ligand metal complexes and applications in catalytic reactions
  • Chiral amino sulfamide ligand metal complexes and applications in catalytic reactions
  • Chiral amino sulfamide ligand metal complexes and applications in catalytic reactions

Examples

Experimental program
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Effect test

Embodiment 1

[0054] The preparation of embodiment 1 compound (L-1)

[0055] Dissolve unilateral protection one, diphenylethylenediamine (4mmol) in ethanol (50mL), slowly add phenol dialdehyde (1.8mmol), react at room temperature for 12h, then add NaBH at 0°C 4 (14.4mmol), after the addition was complete, react at room temperature and monitor by TLC. After the reaction was complete, water (120mL) was added to the reaction solution, and 2 Cl 2 extraction. The organic phase was collected, washed with saturated brine and dried over anhydrous sodium sulfate; concentrated under reduced pressure, separated and purified by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain the ligand compound (L-1).

[0056] The synthetic route of compound (L-1) is as follows:

[0057]

[0058] Referring to Example 1, compounds L1-L8 were prepared. The specific structural analysis data and physical and chemical parameters of L1-L8 are as follows.

[0059] L1: white solid; [α] D 25 =-...

Embodiment 2

[0067] The preparation of embodiment 2 formula (I-1)

[0068] The chiral sulfamoamide ligands (L1-L8) prepared in the above examples were used to prepare the formula (I-1) according to the following route and operation steps. The specific route is:

[0069]

[0070] ; The specific operation is: add nickel acetate (0.02mmol), chiral aminosulfonamide ligand (0.01mmol), tetrahydrofuran (4mL) and a stir bar into the reaction vessel, and stir at 35°C for 1.5h.

[0071] Ar is p-nitrophenyl (4-NO 2 -C 6 h 4 ) as an example, that is, the chiral aminosulfonamide ligand L4 as an example, the molecular weight of the complex structural formula is obtained through simulation to be 1157.15115, while the molecular weight obtained in the actual characterization test is 1157.15010, which is basically consistent. It can be seen that the structure of the complex is inferred that the ratio of chiral sulfamoamide ligand L to nickel acetate is 1:2.

Embodiment 3

[0075] A metal complex formed by chiral sulfamoamide ligand L and nickel acetate catalyzes the direct Mannich reaction of benzenesulfonimide and diethyl malonate. .

[0076] Concrete reaction route is as follows:

[0077]

[0078] ; Specific operation steps: Add nickel acetate (0.02mmol), chiral sulfamoamide ligand L (0.01mmol), tetrahydrofuran (4mL) and a stirrer into a reaction vessel, and stir at 35°C for 1.5h. Then add benzenesulfonimide 1a (1mmol), tetrahydrofuran (0.5mL), stir at 0°C for 0.5h, then add diethyl malonate (1mmol) and tetrahydrofuran (0.5mL), stir at 0°C for 16h -17h, TLC detection reaction. Separation and purification by column chromatography, the enantiomeric excess of the product was determined by high performance liquid chromatography (Daicel chiralcel IA, V 正己烷 :V 异丙醇 =70:30, flow rate 1.0mL / min) to collect the target compound 2a. [α] 25 D =+29.6 (c=0.69in CH 2 Cl 2 ); 1 H NMR (500MHz, CDCl 3 )δ7.49(d, J=7.70Hz, 2H), 7.10(s, 5H), 7.04(d, J...

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Abstract

The invention discloses a class of chiral amino sulfamide ligand metal complexes and applications in catalytic reactions, wherein the chiral amino sulfamide ligand metal complex has a structure defined in the specification, R3 is C1-6 alkyl, Ar is aryl, and M is a divalent metal nickel ion, a divalent metal iron ion, a divalent metal copper ion, a divalent metal cobalt ion, a divalent metal zinc ion, a divalent metal manganese ion, a trivalent metal manganese ion or a monovalent metal copper ion. According to the present invention, in the asymmetric direct Mannich reaction for catalyzing imine, the N-sulfonyl-beta-amino acid derivative can be obtained while the chiral amino sulfamide ligand metal complex can have advantages of low consumption, good chemical selectivity and good enantioselectivity.

Description

technical field [0001] The invention relates to a chiral aminosulfonamide ligand metal complex, a preparation method thereof and an application in catalytic Mannich reaction. Background technique [0002] The Mannich reaction (Mannich reaction, referred to as Man's reaction), also known as the amine methylation reaction, is the condensation of a compound (usually a carbonyl compound) containing active hydrogen with formaldehyde and a secondary amine or ammonia to form a β- Organic chemistry reactions of amino (carbonyl) compounds. The asymmetric Mannich reaction between imines and carbonyl compounds is generally regarded as an important method for the synthesis of chiral nitrogen-containing compounds, and it is also one of the most efficient reactions for the formation of C–C. In the synthetic process of asymmetric Mannich reaction, catalyst plays a very important role. In the past two decades, bimetallic catalysis has emerged as an effective method for catalyzing asymmetr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/04C07C311/18C07C311/19C07C303/40B01J31/22
CPCB01J31/2217B01J2231/321B01J2531/0252B01J2531/847C07B2200/07C07C303/40C07C311/18C07F15/045
Inventor 周辉张仕雄邓萍刘谋雄梁国娟黎洋
Owner CHONGQING MEDICAL UNIVERSITY
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