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1, 4-dihydropyridine bifunctional chiral catalyst and preparation method and application thereof

A dihydropyridine and catalyst technology, which is applied in the directions of organic compound/hydride/coordination complex catalyst, carbon-based compound preparation, chemical instruments and methods, etc. Recycling, difficult to control hybrid effects, etc., to avoid transition metal residues, easy to regenerate and reuse, and good application value

Inactive Publication Date: 2019-05-31
广西九圣新材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the asymmetric transfer hydrogenation reaction of HEHs needs the help of other chiral additives to work together
However, the hybridization of the two systems is usually difficult to control, requiring a large amount of chiral additives, and the chiral catalyst is difficult to recover and recycle.

Method used

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  • 1, 4-dihydropyridine bifunctional chiral catalyst and preparation method and application thereof
  • 1, 4-dihydropyridine bifunctional chiral catalyst and preparation method and application thereof
  • 1, 4-dihydropyridine bifunctional chiral catalyst and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] 1. Molecular structural formula of (3R,5S)-5-trityl-1,3-dihydroxypyrrolidine:

[0052]

[0053] 2. Preparation: Slowly drop 1M tetrabutylammonium fluoride solution in tetrahydrofuran (4mL, 4mmol) into (2S,4R)-4-dimethyltert-butylsilyloxy-2-triphenyl-1-hydroxy A solution of pyrrolidine (459.7 mg, 1 mmol) in dry THF (10 mL). The reaction was vigorously stirred at room temperature for 10 hours, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography (the volume ratio of n-hexane:ethyl acetate was 20:1) to obtain white (3R,5S)-5-trityl Base-1,3-dihydroxypyrrolidine solid 338mg (III), yield 98%.

[0054] 3. Structural identification: the obtained compound structure was verified by nuclear magnetic resonance ( 1 (H-NMR) characterization result is: 1 H NMR (400MHz, CDCl 3 )δ7.39(t, J=8.4Hz, 6H), 7.31(t, J=8.4Hz, 3H), 7.19(d, J=8.4Hz, 6H), 6.88(brs, 1H), 5.26(brs, 1H), 4.37(t, J=9.6Hz, 1H), 3.95-3.93(m, 1H), 2.69(dd, J...

Embodiment 2

[0056] 1. The molecular structural formula of (3R,5S)-1-hydroxy-3-acetoacetoxy-5-triphenylmethylpyrrolidine:

[0057]

[0058] 2. Preparation: Add 2,2,6-trimethyl-1,3-dioxin-4-one (142.2 mg, 1 mmol) dropwise to (3R,5S)-5-trityl-1, In a solution of 3-dihydroxypyrrolidine (345.4 mg, 1 mmol) in xylene (0.5 mL) at 130°C. The acetone formed was distilled off from the reaction mixture. Stirring was continued at 130°C for 2 hours, the reaction mixture was cooled to 50°C and the solvent was removed in vacuo. The crude product was purified by silica gel column chromatography (the volume ratio of n-hexane:ethyl acetate was 20:1) to obtain 365 mg of light yellow solid compound (IV), with a yield of 85%.

[0059] 3. Structural identification: the obtained compound structure was verified by nuclear magnetic resonance ( 1 (H-NMR) characterization result is: 1 H NMR (400MHz, CDCl 3 )δ7.43(t, J=8.4Hz, 6H), 7.32(t, J=8.4Hz, 3H), 7.18(d, J=8.4Hz, 6H), 6.89(brs, 1H), 4.37(t, J=9.6Hz, 1H...

Embodiment 3

[0061] 1. Molecular structural formula of (3R,5S)-1-hydroxy-3-isobutyrylacetoxy-5-triphenylmethylpyrrolidine:

[0062]

[0063] 2. Preparation: Add 2,2-dimethyl-6-isopropyl-1,3-dioxin-4-one (170.2mg, 1mmol) dropwise to (3R,5S)-5-trityl In a solution of 1,3-dihydroxypyrrolidine (345.4mg, 1mmol) in xylene (0.5mL) at 130°C. Stirring was continued at 130°C for 2 hours, the reaction mixture was cooled to 50°C and the solvent was removed in vacuo. The crude product was purified by silica gel column chromatography (the volume ratio of n-hexane:ethyl acetate was 20:1) to obtain 297 mg of light yellow solid compound (IV), with a yield of 65%.

[0064] 3. Structural identification: the obtained compound structure was verified by nuclear magnetic resonance ( 1 (H-NMR) characterization result is: 1 H NMR (400MHz, CDCl3) δ7.40(t, J=8.4Hz, 6H), 7.31(t, J=8.4Hz, 3H), 7.16(d, J=8.4Hz, 6H), 6.90(brs, 1H ), 4.36(t, J=9.6Hz, 1H), 3.95-3.92(m, 1H), 3.46(s, 2H), 2.71(dd, J=11.6, 6.0Hz, 1H),...

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Abstract

The invention belongs to the field of organic catalysis, and discloses a novel 1, 4-dihydropyridine bifunctional chiral catalyst and a preparation method and application thereof. The general chemicalstructure formula of the chiral catalyst is shown in formula (I) as shown in specification. According to the invention, a 1, 4-dihydropyridine derivative and a chiral tetrahydropyrrole derivative areused as raw materials, and finally, the novel 1, 4-dihydropyridine bifunctional chiral catalyst is synthesized. The method has mild synthesis reaction conditions and high yield. The operation steps are simple, safe and reliable; the catalyst is environment-friendly, and can be applied to the fields of asymmetric catalytic transfer hydrogenation, chiral fine chemical synthesis, chiral drug or drugintermediate synthesis, chiral new materials, chiral functional molecule synthesis and the like; and the application prospect is wide.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry and catalysis, and more specifically relates to a novel 1,4-dihydropyridine bifunctional chiral catalyst and its preparation method and application. Background technique [0002] Asymmetric catalytic hydrogenation is an important direction of modern synthetic chemistry. The traditional asymmetric catalytic hydrogenation reaction uses hydrogen as the reducing agent and performs asymmetric catalytic hydrogenation based on transition metal chiral catalysts. Isopropanol and formic acid are commonly used hydrogen sources in asymmetric transfer catalytic hydrogenation reactions. Although the catalytic process of these transition metals shows good reactivity and selectivity, however, the reaction still has great limitations, such as: the type of substrate is limited, that is, the scope of the substrate is narrow; the catalyst is difficult to remove and recycle; The use of high-pressure hydr...

Claims

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Application Information

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IPC IPC(8): C07D401/14B01J31/02C07C47/228C07C45/62C07C255/56C07C253/30C07C205/44C07C201/12C07C47/24C07C47/23
Inventor 周杰峰
Owner 广西九圣新材料有限公司
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