Cycloglutaramide-based ligand, synthetic method of ligand, application of ligand in coupling reaction for synthesizing arylamine derivative and catalytic system

Abstract

The invention discloses a cycloglutaramide-based ligand having a general formula I shown in the specification, a synthetic method of the ligand, an application of the ligand in a coupling reaction forsynthesizing an arylamine derivative, and a catalytic system. The compounds represented by the formula I can be used as a ligand in the coupling reaction of synthesizing the arylamine derivative by using an aryl halide under catalysis of copper, especially the coupling reaction of aryl halide and an amine source to form a C-N bond under catalysis. Under mild reaction conditions, the high-yield arylamine derivative is obtained, and the ligand has a simple structure, convenient preparation and a less use amount.

Description

technical field [0001] The invention relates to a cyclopentanamide ligand, a synthesis method, an application in a coupling reaction of synthesizing arylamine derivatives, and a catalytic system. Background technique [0002] The traditional method of forming C-N, C-C, C-O, C-S bonds is generally nucleophilic substitution, but the substitution on the aromatic ring is more difficult, and generally requires high temperature and high pressure. However, transition metal-catalyzed aryl halides and suitable nucleophiles such as organic amines, active methylene groups, phenols, alcohols, and thiophenols undergo corresponding coupling reactions to form C-N, C-C, and more efficiently and gently. C-O, C-S keys. [0003] Generally, the reactivity of aryl iodide and aryl bromide is high, and the oxidative addition of transition metals to them is easy to carry out. Under the catalysis of transition metals such as palladium, copper, nickel, etc., they can be better Carry out the corresp...

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Problems solved by technology

[0007] 1. Teng ligands or azacarbene ligands with large steric hindrance and complex structures need to be added to the system to promote the reaction. The synthesis of these ligands is relatively cumbersome and the conditions are relatively stringent;

[0008] 2. The price of palladium catalyst is expensive, and the reaction operation required by zero-valent nickel is quite harsh, which limits its application to a certain extent

However, the reported substrates for copper-catalyzed coupling reactions are mostly limited to iodides and bromides.

[0009] In 2008, Sukbok Chang's group used ammonia water and ammonium chloride as ammonia sources, and used L-proline at room temperature to realize the coupling reaction of aryl iodide and ammonia water or ammonium chloride. Both ammonia water and ammonium chloride as amine sources can be Coupling products are obtained in good yields, however this method is only applicable to aryl iodides and does not involve the more common aryl chloride and aryl bromide substrates

[0011] Xia, N; Tailler, M et al. used 2,4-pentanedione as a ligand to realize the C-N coupling of aryl bromide and ammonia water. The main disadvantage of this system is that by-products of C-C coupling will be produced, which reduces the reaction economy

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