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Axially chiral imidazole salt compound and preparation method thereof

A technology of axial chirality and imidazolium salt, which is applied in the field of synthesis of chiral catalysts, can solve the problems of chiral azacarbene synthesis, difficulty in synthesis, limitation of synthesis and application of new axial chiral azacarbene, etc., and achieve novel structure , Synthesis is simple and convenient, good effect of asymmetric selection

Inactive Publication Date: 2011-05-25
SOUTH CHINA UNIV OF TECH
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Problems solved by technology

[0004] However, due to the difficulty in the synthesis of chiral azacarbenes, especially the synthesis of axial chiral imidazolium salts or axial chiral azacarbenes, the synthesis and application of new axial chiral azacarbenes are greatly limited.
At present, only a few axial chiral imidazolium salts or axial chiral azacarbenes have been reported, and there are few reports on axial chiral imidazolium salts or axial chiral azacarbenes with independent intellectual property rights in my country.

Method used

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  • Axially chiral imidazole salt compound and preparation method thereof
  • Axially chiral imidazole salt compound and preparation method thereof
  • Axially chiral imidazole salt compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Preparation of 1,3-bis{2-[2'-methoxy-((R)-(+)-1,1'-naphthyl)]}imidazolium salt (I-1)

[0028]

[0029] Dissolve compound N1, N2-bis{(R)-(+)-2′-methoxy-[1,1′-naphthyl]}-1,2-ethylenediamine in MeOH / HCl=12ml / The acidification reaction was carried out in 1 ml of the mixed solution, which was stirred and reacted at room temperature for 1 hour. After it was cooled to room temperature, the solvent was distilled off under reduced pressure to obtain a yellow solid, and then the obtained yellow solid was mixed with P 2 o 5 Dry in a desiccator for 3 hours. Afterwards, the above yellow solid was dissolved in 5ml HC(OEt) under nitrogen protection 3 , react at 80°C for 1 hour. After it was cooled to room temperature, the precipitated solid was filtered and washed with Et 2 O washing. The obtained solid is the product after drying, with a yield of 67%. The melting point is 216°C.[α] 20 D =+80.0 (measurement concentration c=0.1, measurement solvent is CH 2 Cl 2 ). 1 H NM...

Embodiment 2

[0031]Preparation of 1,3-bis{2-[2'-hydroxyl-((R)-(+)-1,1'-naphthyl)]}imidazolium salt (V-2a)

[0032]

[0033] Taking compound N1, N2-bis{(R)-(+)-2'-methoxymethyl ether-[1,1'-naphthyl]}-1,2-ethylenediamine as raw material, its Dissolve in MeOH / HCl=12ml / 1ml, and reflux and stir at 80°C for 5 hours. After it was cooled to room temperature, the solvent was evaporated under reduced pressure, and then 2 o 5 Dry in a desiccator for 6 hours to obtain a yellow solid. Afterwards, the above yellow solid was dissolved in 5ml HC(OEt) under nitrogen protection 3 , reacted at 130°C for 6 hours, and after cooling to room temperature, the precipitated solid was filtered and washed with Et2O. The resulting solid was dried and the product yield was 70%. Its physical constants are: melting point is 221°C; [α]20D+31.0 (measured concentration c=0.1, measured solvent is DMSO). 1 H NMR (DMSO, 400MHz): δ3.65-3.70 (2H, m), 1.00 (3H, d, J=6.8Hz), 6.77 (2H, d, 8.4Hz), 7.10 (2H, d, 8.4Hz) , 7.2...

Embodiment 3

[0035] Preparation of 1,3-bis[2-((R)-(+)-1,1'-naphthyl)]imidazolium salt (I-3)

[0036]

[0037] The preparation method is the same as in Example 1, with compound N1, N2-two {(R)-(+)-[1,1'-naphthyl]}-1,2-ethylenediamine as raw material, the product yield is 61%. Its physical constants are: melting point is 200°C. [α]20D=+27.0 (measured concentration c=0.1, measured solvent is DMSO). 1 H NMR (DMSO, 400MHz): δ3.01 (2H, s), 3.72 (2H, s), 7.02-7.04 (4H, m), 7.27-7.76 (14H, m), 8.15-8.24 (8H, m) , 9.07 (1H, s).13C NMR (DMSO, 100MHz): δ51.4, 123.1, 124.8, 125.8, 126.0, 126.1, 126.6, 127.3, 127.4, 127.8, 128.3, 128.7, 129.2, 130.0, 131.5, 132.2, 132.3, 132.5, 132.7, 133.2, 158.4. Infrared spectrum IR (KBr) vmax 3422.2, 1614.0, 1589.2, 1504.8, 1265.4, 1007.0, 806.8, 784.0, 750.8cm-1. The calculated value of high resolution mass spectrum HRMS (ESI) ([M+H]+) is C43H31N2+1: 575.2482, and the actual measured value is 575.2481.

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Abstract

The invention provides an axially chiral imidazole salt compound and a preparation method thereof. The axially chiral imidazole salt compound has a structural formula shown in the specifications. The technical scheme of the preparation method comprises the following steps of: dissolving a binaphthyl axially chiral imidazole diamine compound in an alcohol acid mixed solvent for acidification, and removing the solvent by evaporation so as to obtain a solid intermediate product; drying the solid intermediate product in a drier which contains P2O5, and dissolving in raw acid trialkyl ester for reaction under the protection of inert gas; and after the reaction is finished, cooling reaction liquid to room temperature, precipitating a solid product, filtering the solid product, and washing with Et2O. The alcohol is absolute methanol or absolute ethanol; and the acid is any one of haloid acid, HBF4, HPF6 or HOTf. The axially chiral imidazole salt compound can be applied to asymmetric oxidation reactions, asymmetric coupling reactions and asymmetric addition reactions.

Description

technical field [0001] The invention relates to the technical field of synthesis of chiral catalysts, in particular to an axial chiral imidazolium salt compound and a preparation method thereof. Background technique [0002] The azacarbene produced by imidazolium salt can not only be used as an organic catalyst for asymmetric organic catalysis, but also has a very strong coordination ability with metals, and can coordinate with most transition metals to form azacarbene metal complexes. Metal complexes are widely used in various catalytic reactions. In addition, the precursor imidazolium salt of azacarbene has good stability, it is very stable to air and humidity, and more importantly, it can be well supported as a catalyst for industrial catalysis. It is worth noting that the chiral azacarbene produced by chiral imidazolium salts has good performance in terms of catalytic performance and asymmetric selectivity, especially the axial chiral azacarbene has excellent asymmetric...

Claims

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Application Information

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IPC IPC(8): C07D233/06C07F9/6506
Inventor 祝诗发王朝
Owner SOUTH CHINA UNIV OF TECH
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