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Axial chiral imidazole salt compound and preparation method thereof

An axial chirality and compound technology, applied in the field of chiral catalysts, can solve the problems of restricting the synthesis and application of new axial chiral azacarbenes, synthesis difficulties, chiral azacarbene synthesis difficulties, etc., and achieve high asymmetric selectivity , the effect of easy availability of raw materials and high product yield

Inactive Publication Date: 2012-06-13
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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  • Axial chiral imidazole salt compound and preparation method thereof
  • Axial chiral imidazole salt compound and preparation method thereof
  • Axial chiral imidazole salt compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] 1,3-bis{3-[2-methyl, 2′-hydroxy-((R)-(+)-1,1′-naphthyl)]}benzimidazole salt (IM-I-2) preparation:

[0042]

[0043] (1) Preparation of 3-halo-2-methyl, 2'-methoxymethyl ether-(R)-(+)-1,1'-binaphthalene (I-2): at room temperature, Dissolve 2-methyl, 2'-methoxymethyl ether-(R)-(+)-1,1'-binaphthalene (1.95g, 5mmol) in 80ml of ether, add butyllithium (4.17 ml, 2.4M), the reaction system reacted at room temperature for 4 hours. Afterwards, a tetrahydrofuran solution of iodine (2.54 g, 10 mmol dissolved in 20 ml tetrahydrofuran) was added at 0° C., and the reaction was continued at room temperature for 4 hours after the addition was completed. Thereafter, the reaction was extracted with saturated aqueous sodium sulfite solution, extracted three times with ethyl acetate, and finally washed with saturated brine. Afterwards, it was dried with anhydrous magnesium sulfate, separated by column chromatography, and the eluent was petroleum ether / ethyl acetate=20 / 1, and 3-halo-2...

Embodiment 2

[0049] 1,3-bis{3-[2-phenyl, 2′-hydroxyl-((R)-(+)-1,1′-naphthyl)]}benzimidazole salt (IM-I-1) preparation:

[0050]

[0051] 1,3-bis{3-[2-phenyl, 2′-hydroxyl-((R)-(+)-1,1′-naphthyl)]}benzimidazole salt (IM-I-1) The preparation takes 3-halo-2-phenyl, 2'-methoxymethyl ether-(R)-(+)-1,1'-binaphthalene (I-1) as raw material, and the remaining steps are the same as 1, Preparation method of 3-bis{3-[2-methyl, 2′-hydroxyl-((R)-(+)-1,1′-naphthalene)]}benzimidazolium salt (IM-I-2) Same, the final product (IM-I-1) yield of this embodiment is 63%. Its physical constants are: melting point is 321°C; [α] 20 D =+191.0 (measurement concentration c=0.1, measurement solvent is CH 2 Cl 2 ). 1 HNMR (DMSO, 400MHz): δ6.73 (2H, s), 7.06 (2H, d, 4Hz), 7.24-7.33 (14H, m), 7.44 (8H, s), 7.57-7.60 (2H, m), 7.67-7.73(2H, m), 7.99(2H, m), 8.13(2H, d, 8Hz), 8.21(2H, d, 8Hz), 8.44(2H, s), 9.74(2H, s), 10.79( 1H, s). 13 CNMR (DMSO, 100MHz): δ113.9, 122.0, 122.2, 123.9, 124.6, 124.7, 125.8, 126.0...

Embodiment 3

[0053] 1-phenyl, 3-{3-[2-methyl, 2′-hydroxyl-((R)-(+)-1,1′-naphthyl)]}benzimidazole salt (IM-II-1 ) preparation:

[0054]

[0055] (1)N 1 -[3-(2-phenyl, 2-methyl ether binaphthyl)]-1, the preparation of 2-o-phenylenediamine (III-1):

[0056] Under nitrogen protection, add a magnetic stir bar to a dry schlenk tube, add raw materials 2-phenyl, 2'-methoxymethyl ether, 3'-halo-(R)-(+)-1,1'- Add Pd(OAc) to binaphthyl (I-1) (516mg, 1.0mmol), ortho-phenylenediamine (108mg, 1.0mmol) 2 (22.5mg, 0.1mmol), BINAP (124.5g, 0.2mmol), Cs 2 CO 3 (626mg, 2.0mmol), 15ml solvent 1,4-dioxane, and the mixture was reacted at 100°C for 14 hours. After the reaction system was cooled to room temperature, the solid impurities in the system were filtered off, the filtrate was washed with saturated brine, dried with anhydrous sodium sulfate, and then separated by column chromatography, and the eluent was petroleum ether / ethyl acetate= 7 / 1. Finally, a yellow solid product was obtained with a yie...

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Abstract

The invention provides an axial chiral imidazole salt compound and a preparation method thereof. The structural formula of the axial chiral imidazole salt compound is that a binaphthol derivative and halogen reacts firstly to obtain a intermediate product which is coupled with o-phenylenediamine to obtain a single substituted axial chiral o-phenylenediamine compound and a axial chiral o-phenylenediamine compound with symmetrical C2. The single substituted axial chiral o-phenylenediamine compound and a heterocyclic aromatic halogenated compound or an aryl trifluoroacetic acid ester compound react to obtain an intermediate product, and the intermediate product and ortho-acid trialkyl ester react to obtain the axial chiral imidazole salt compound with R3 which is aryl. The single substituted axial chiral o-phenylenediamine compound and the ortho-acid trialkyl ester react to obtain a intermediate product, the intermediate product and a halogenated alkyl compound react to obtain the axial chiral imidazole salt compound with R3 which is alkyl. The axial chiral imidazole salt compound preparation method is high in synthesis yield, raw materials are cheap and easy to obtain, and the chiral center of the obtained axial chiral imidazole salt compound is close to a reaction point, thereby being favorable for obtaining high asymmetrical selective results.

Description

technical field [0001] The invention relates to a chiral catalyst, in particular to an axial chiral imidazolium salt compound and a preparation method thereof. Background technique [0002] The azacarbene produced by the imidazolium salt as the precursor of the azacarbene is not only used in asymmetric organocatalysts, but also complexed with metals for asymmetric organocatalysis. Because of its strong ability to coordinate with metals, it can coordinate with most transition metals to form azacarbene metal complexes, and its 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 from chiral imidazolium salts has good performance in terms of catalytic performance and asymmetric selectivity. The complex formed b...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D235/06C07D405/04C07D401/04C07D401/06C07D405/06C07D409/06C07D401/14C07F9/6506
Inventor 祝诗发王朝胡浪肖晔林张智才
Owner SOUTH CHINA UNIV OF TECH
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