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Asymmetric synthesis method of chiral bicyclocaprolactam compounds

A technology of caprolactam and synthesis method, which is applied in the direction of organic chemistry, can solve the problems of limited application range, environmental pollution, and difficult removal of metals, and achieve the effect of reducing purification steps and increasing product yield

Active Publication Date: 2017-01-04
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Catalytic asymmetric synthesis is the most effective way to achieve asymmetric value-added and obtain optically active substances by chemical means, including a small amount of enzyme-catalyzed reactions and most of the chemical reactions catalyzed by metal-chiral ligands, but enzyme-catalyzed High specificity limits its application range, and in the metal-catalyzed reaction system, the metals involved in the reaction are difficult to remove after the reaction, which is very easy to cause pollution to the environment

Method used

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  • Asymmetric synthesis method of chiral bicyclocaprolactam compounds
  • Asymmetric synthesis method of chiral bicyclocaprolactam compounds
  • Asymmetric synthesis method of chiral bicyclocaprolactam compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Example 1: (1R,2R,3R,5S)-1-hydroxy-2-methyl-3,6-diphenyl-8-oxo-6-azabicyclo[3,2,1]octane Preparation of -7-one

[0053] Add 2-carbonyl-N-phenylbutyramide (0.0354g, 0.2mmol), cinnamaldehyde (0.0328g, 0.24mmol) and 0.5mL toluene in 10mL test tube, in chiral secondary amine catalyst (VI) (0.017g, 0.04 mmol) and triethylamine (0.004g, 0.04mmol) were reacted at 0°C for 48h under the co-catalysis, extracted with ethyl acetate (3×2mL), after the extract was distilled to remove the solvent, the obtained concentrate was washed with 200-300 mesh silica gel Carry out column chromatography separation, eluent is the mixed solution of ethyl acetate and petroleum ether volume ratio 1:3, collect the eluate containing target compound, concentrate and dry to obtain target compound (0.0494g, yield 80%, Ee value 99%, 98%, dr value 5.7:1), 1 H NMR (500MHz, CDCl 3 ):δ=7.596-7.580(m,2H),7.396-7.364(m,2H),7.334-7.304(m,2H),7.249-7.144(m,4H),5.951(s,1H),4.584(s ,1H),3.295-3.250(m,1H),2.480-...

Embodiment 2

[0054] Example 2: (1R,2R,3R,5S)-1-hydroxy-2-methyl-3,6-diphenyl-8-oxo-6-azabicyclo[3,2,1]octane Preparation of -7-one

[0055] Add 2-carbonyl-N-phenylbutyramide (0.0354g, 0.2mmol), cinnamaldehyde (0.0328g, 0.24mmol) and 0.5mL toluene in 10mL test tube, in chiral secondary amine catalyst (IV) (0.013g, 0.04 mmol) and triethylamine (0.004g, 0.04mmol) were reacted at 25°C for 24h under the co-catalysis, extracted with ethyl acetate (3×2mL), after the extract was distilled to remove the solvent, the obtained concentrate was washed with 200-300 mesh silica gel Carry out column chromatography separation, eluent is the mixed solution of ethyl acetate and petroleum ether volume ratio 1:3, collect the eluent containing target compound, concentrate and dry to obtain target compound (0.0488g, yield 79%, Ee value 94%, 97%, dr value 2.8:1).

Embodiment 3

[0056] Example 3: (1R,2R,3R,5S)-1-hydroxy-2-methyl-3,6-diphenyl-8-oxo-6-azabicyclo[3,2,1]octane Preparation of -7-one

[0057] Add 2-carbonyl-N-phenylbutyramide (0.0354g, 0.2mmol), cinnamaldehyde (0.0328g, 0.24mmol) and 0.5mL toluene in 10mL test tube, in chiral secondary amine catalyst (IV) (0.015g, 0.04 mmol) and triethylamine (0.004g, 0.04mmol) were reacted at 25°C for 24h under the co-catalysis, extracted with ethyl acetate (3×2mL), after the extract was distilled to remove the solvent, the obtained concentrate was washed with 200-300 mesh silica gel Carry out column chromatography separation, eluent is the mixed solution of ethyl acetate and sherwood oil volume ratio 1:3, collect the eluent containing target compound, concentrate and dry to obtain target compound (0.050g, yield 81%, Ee value 95%, 95%, dr value 2.5:1).

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Abstract

The invention provides an asymmetric synthesis method of a chiral bicyclo-caprolactam compound as shown in a formula (I). The asymmetric synthesis method comprises the following steps of: mixing a chiral secondary amine catalyst, an alkaline substance and an organic solvent; adding alpha,beta-unsaturated carbonyl compound as shown in a formula (II) and an alpha-carbonyl amide ramification as shown in a formula (III) under the condition of stirring, and reacting at -20 DEG C -60 DEG C for 12-84 hours; and after the reaction is finished, carrying out post treatment on reaction liquid to obtain the chiral bicyclo-caprolactam compound as shown in a formula (I). The chiral bicyclo-caprolactam compound has chirality; the asymmetric synthesis method provided by the invention omits the purifying step through adoption of a one-pot method, enhances the product yield, is especially suitable for industrial production and can be applied to the fields of organic synthesis, materials and the like.

Description

[0001] (1) Technical field [0002] The invention relates to an asymmetric synthesis method of chiral bicyclocaprolactam compounds. [0003] (2) Background technology [0004] Catalytic asymmetric synthesis is the most effective way to achieve asymmetric value-added and obtain optically active substances by chemical means, including a small amount of enzyme-catalyzed reactions and most of the chemical reactions catalyzed by metal-chiral ligands, but enzyme-catalyzed High specificity limits its scope of application, and in metal-catalyzed reaction systems, the metals involved in the reaction are difficult to remove after the reaction, which can easily pollute the environment. Organic small molecule catalysis realizes the high-efficiency asymmetric catalytic synthesis of chiral substances by simulating enzyme catalysis, and overcomes the shortcomings of high specificity of enzyme catalysis with its wide universality. The toxicity residue problem caused by the application of meta...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D498/08
CPCC07D498/08
Inventor 夏爱宝吴超许丹倩徐振元
Owner ZHEJIANG UNIV OF TECH
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