Asymmetric hydrogenation synthetic method of chiral aromatic amine compound with high steric hindrance

An aromatic amine, asymmetric technology, applied in the field of synthesis of high sterically hindered chiral aromatic amine compounds, can solve the problems of low reactivity, harsh reaction conditions, narrow substrate range, etc., and achieve high reactivity, mild reaction conditions and high activity Effect

Inactive Publication Date: 2014-02-12
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, in the asymmetric hydrogenation reaction of highly hindered imines, there are mainly problems such as low reactivity, narrow substrate range, and harsh reaction conditions. The asymmetric hydrogenation method of imine is of great significance

Method used

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  • Asymmetric hydrogenation synthetic method of chiral aromatic amine compound with high steric hindrance
  • Asymmetric hydrogenation synthetic method of chiral aromatic amine compound with high steric hindrance
  • Asymmetric hydrogenation synthetic method of chiral aromatic amine compound with high steric hindrance

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Under nitrogen protection, [Ir(COD)Cl] 2 (0.0025mmol, 0.5mol%), chiral phosphine-phosphoramidite ligand (0.0055mmol, 1.1mol%) and KI (0.025mmol, 5.0mol%) were dissolved in dichloromethane (1.0mL), stirred at room temperature For 10 minutes, a solution of the substrate (E)-2,6-dimethyl-N-(1-phenylethylidene)aniline (0.5 mmol) in dichloromethane (1.0 mL) was added, and it was subjected to high pressure reaction In the kettle, the hydrogen gas was replaced 3 times, and then the hydrogen gas was fed to 20 atmospheres, and the reaction was carried out at room temperature for 24 hours. Slowly release hydrogen gas, remove the solvent and separate with a silica gel column to obtain the product 2,6-dimethyl N-(1-phenylethyl)aniline with a yield of 98% and ee of 97%. HPLC (chiralcel OJ-H, n-hexane / i-PrOH=90 / 10, 1.0mL / min, 254nm, 40°C):t R (major)=4.9min,t R (minor)=5.4min.[α] D 25 =-158(c=1.42in CHCl 3 ). 1 H NMR (400MHz, CDCl 3 ):δ=1.54(d,J=6.8Hz,3H),2.19(s,6H),3.22(br,1...

Embodiment 2

[0039] Using KI in Example 1 with I 2 Instead, the rest is the same as in Example 1, and the product 2,6-dimethyl-N-(1-phenylethyl)aniline is obtained in a 98% yield and 96% ee.

Embodiment 3

[0041] With the reaction condition H among the embodiment 1 2 The pressure was changed to 60 atmospheres, and the rest was the same as in Example 1. The product 2,6-dimethyl N-(1-phenylethyl)aniline was reacted with a yield of 98% and 97% ee.

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Abstract

The invention relates to an asymmetric hydrogenation synthetic method of a chiral aromatic amine compound of iridium-catalyzed imine with high steric hindrance. The catalyst adopted is a catalyst generated by in-situ reaction of a 1, 5-cyclooctadiene iridium chloride dimer and a chiral phosphine-phosphoramidite ligand. The reaction can be carried out under the following condition: the additives comprise iodine, potassium iodide and tetrabutyl ammonium iodide; the temperature is 0-200 DEG C; the solvent is dichloromethane, 1, 2-dichloroethane to the like; the pressure is 10-100 barometric pressures; the time is 12-48 hours; and the proportion of a primer and the catalyst can reach 100000/1. The method provided by the invention has the characteristics of mild reaction condition, high activity, high stereoselectivity, wide application range of the primer and the like.

Description

technical field [0001] The invention relates to an iridium-catalyzed asymmetric hydrogenation method of high-steric hindered imines, and the method is used to synthesize high-steric hindered chiral aromatic amine compounds with high activity and high stereoselectivity. Background technique [0002] Chiral amine compounds are important intermediates in organic synthesis and can be used to prepare various natural and non-natural compounds with biological activity. In recent years, the preparation of chiral amine compounds by asymmetric catalytic hydrogenation of imines has achieved great success [(a) H.-U. Blaser, F. Spinder in Handbook of Homogeneous Hydrogenation (Eds.: J.G.de Vries, C.J. Elsevier), Wiley-VCH, Weinheim, 2007, pp.1193; (b) C.Claver, E.Fernandez in Morden Reduction Methods (Eds.: P.Anderson, I.Munslow), Wiley-VCH, Weinheim, 2008, pp.237; (c) H.-U. Blaser, F. Spinder in Comprehensive Asymmetric Catalysis (Eds.: E. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, B...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B53/00C07C209/52C07C211/48C07C213/02C07C217/08C07C217/84C07C229/18C07C227/06C07C235/16C07C231/12
Inventor 胡向平侯传金
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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