Asymmetric catalytic hydrogenation method for ketone-derived N-alkylimine

A technology for catalytic hydrogenation of alkylimines, applied in chemical instruments and methods, preparation of amino compounds, preparation of amino hydroxyl compounds, etc., can solve the problems of failing to meet the requirements of industrialization and low enantioselectivity

Inactive Publication Date: 2011-05-11
INST OF CHEM CHINESE ACAD OF SCI
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Problems solved by technology

In this article, only the asymmetric catalytic hydrogenation of aromatic ketone-derived acyclic N-alkylimines is discussed, and alkylketone-derived acyclic N-alkylimine substrates are not included; and aromatic The enantioselectivity of the asymmetric catalytic hydrogenation of ketone-derived acyclic N-alkylimines is low, and the enantiomeric excess of the product is only 35%-72%, which is far from meeting the requirements of industrialization

Method used

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  • Asymmetric catalytic hydrogenation method for ketone-derived N-alkylimine

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Effect test

Embodiment 1-9

[0068] Embodiment 1-9, the screening of additive and the optimization of additive dosage

[0069] Asymmetric catalytic hydrogenation of N-benzyl-phenylmethylimine from the reaction of acetophenone with benzylamine as a model reaction under the catalysts (R,R)-3a and (R,R)-4e , Carried out the screening of asymmetric catalytic reaction additives and the optimization of additive dosage, the experimental design and result of specific embodiment 1-9 are shown in Table 1.

[0070] The specific operation of the asymmetric catalytic hydrogenation reaction is as follows: the hydrogenation experiments were all carried out in a high-pressure reactor. The molar dosage is the catalyst of reaction substrate N-benzyl-phenylmethylimine 2%, the reaction substrate N-benzyl-phenylmethylimine of 0.2mmol, a certain amount of additives are dissolved in 1mL solvent , After replacing the gas with nitrogen, fill it with 50atm hydrogen, and react at 40°C for a certain period of time. In this reactio...

Embodiment 10-27

[0076] Embodiment 10-27, the screening of catalyst

[0077] Taking the asymmetric catalytic hydrogenation of N-benzyl-phenylmethylimine generated by the reaction of acetophenone and benzylamine as a model reaction, the catalysts were screened, and the catalysts used were (R, R)-3~(R , R)-15, the experimental design and results of specific examples 10-27 are shown in Table 2.

[0078]The specific operation of the asymmetric catalytic hydrogenation reaction is as follows: the hydrogenation experiments were all carried out in a high-pressure reactor. The molar dosage is the catalyst of reaction substrate N-benzyl-phenylmethylimine 2%, 0.2mmol reaction substrate N-benzyl-phenylmethylimine and 0.22mmol di-tert-butyl dicarbonate are dissolved in In 1 mL of dichloromethane, replace the gas with nitrogen, fill with 50 atm of hydrogen, and react at 40°C for 10 hours. The types of catalysts used in this reaction are shown in Table 2.

[0079] The stirring was stopped, and the reactio...

Embodiment 28-40

[0085] Embodiment 28-40, screening of asymmetric catalytic hydrogenation reaction solvent

[0086] Taking the asymmetric catalytic hydrogenation of N-benzyl-phenylmethylimine generated by the reaction of acetophenone and benzylamine as a model reaction, the screening of the reaction solvent was carried out. The experimental design and results of specific examples 28-40 are shown in the table 3.

[0087] The specific operation of the asymmetric catalytic hydrogenation reaction is as follows: the hydrogenation experiments were all carried out in a high-pressure reactor. The molar dosage is the catalyst (R, R)-4e of 2% of reaction substrate N-benzyl-phenylmethylimine, 0.2mmol reaction substrate N-benzyl-phenylmethylimine and 0.22mmol Di-tert-butyl dicarbonate was dissolved in 1 mL of reaction solvent, and after the gas was replaced with nitrogen, 50 atm of hydrogen gas was filled in, and the reaction was carried out at 40° C. for 10 hours.

[0088] Among them, the experiment nu...

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Abstract

The invention discloses a method for performing the asymmetric catalytic hydrogenation of ketone-derived N-alkylimine. In the method disclosed by the invention, the catalytic hydrogenation of the ketone-derived N-alkylimine is performed in the presence of a chiral catalyst formed by a chiral diamine ligand and a transitional metal to obtain a chiral amine product with high yield and high enantioselectivity. The enantiomeric excess of a chiral amine product formed by the hydrogenation of an acyclic N-alkylimine substrate may reach 98 percent ee; and the enantiomeric excess of a chiral amine product formed by the hydrogenation of an exocyclic N-alkylimine substrate may reach over 99 percent ee. The method disclosed by the invention realizes the asymmetric catalytic hydrogenation of ketone-derived N-alkylimine with high enantioselectivity, and the obtained chiral amine product is an important medicinal and material intermediate and has a bright actual application prospect.

Description

technical field [0001] The invention relates to a method for asymmetric catalytic hydrogenation of imine compounds, in particular to a method for asymmetric catalytic hydrogenation of ketone-derived N-alkyl imines. Background technique [0002] The asymmetric and efficient synthesis of chiral compounds with high enantioselectivity has attracted increasing attention in the fields of chemical industry, agriculture, animal husbandry and medicine, especially in the pharmaceutical industry. mainstream (A.M.Rouhi, "Chiralchemistry", Chem. Eng. News 2004, 82, 47). Asymmetric catalytic hydrogenation is one of the main methods for the efficient preparation of chiral compounds. Asymmetric catalytic hydrogenation refers to the reaction of chiral catalysts (generally complexes formed by chiral ligands and transition metals, X. Zhang, "New ChiralPhosphorus Ligands for Enantioselective Hydrogenation", Chem.Rev.2003, 103, 3029) Under the action, the addition reaction of hydrogen to the u...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B43/04C07C209/52C07C211/27C07C213/02C07C217/58C07C211/29C07C211/30C07D333/20C07D307/52C07C211/17C07C269/06C07C271/12C07C271/16C07C271/14C07C271/24C07D311/68B01J31/22
Inventor 范青华陈飞何艳梅
Owner INST OF CHEM CHINESE ACAD OF SCI
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