CN102994576A - Method for catalytic synthesis of S-configuration aromatic alcohol by intervention of cyclodextrin - Google Patents
Method for catalytic synthesis of S-configuration aromatic alcohol by intervention of cyclodextrin Download PDFInfo
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Abstract
The invention discloses a method for catalytic synthesis of S-configuration aromatic alcohol by intervention of cyclodextrin, and belongs to the technical field of organic synthesis. A certain amount of cyclodextrin is added to a bio-transformation system for asymmetric reduction of aromatic ketone in entire plant cell catalysis according to molar ratio, so that cyclodextrin and the aromatic ketone form a clathrate compound. Therefore, the solubility of a reaction substrate in water is effectively improved; and the inhibition effects of the substrate and the product on enzyme are reduced. The catalytic reduction efficiency of the entire plant cell is improved by cyclodextrin; the stereoselectivity on the substrate is increased; and the conversion rate of the substrate and the enantiomeric excess value of the product are obviously improved. The dosage of cyclodextrin is added at different molar ratios according to difference of the substrates when the substrate concentration is 60mmol/L; the conversion rate of the substrate aromatic ketone is 57-95%; the enantiomeric excess value of the product S-configuration aromatic alcohol is 85-99%; and the product has high practical application value.
Description
Technical field
A kind of cyclodextrin is got involved the method for the synthetic S-configuration aromatic alcohol of catalytic asymmetric reduction prochirality aromatic ketone, belongs to the technical field of organic synthesis.
Background technology
The optical activity aromatic alcohol is the important intermediate of the chipal compounds such as synthesis of chiral medicine, agricultural chemicals, foodstuff additive, and wherein S-configuration aromatic alcohol is because of more consistent with the nature chiral environment, and it is important especially to seem.With chemical process the prochirality aromatic ketone is carried out the important channel that asymmetric reduction is preparation S-configuration aromatic alcohol, but along with petering out of ore resource and day by day increasing the weight of of environmental pollution, have now efficient single-minded and the application of conversion technology in the asymmetric synthesis green energy conservation characteristics more and more come into one's own.Bio-transformation catalyzer commonly used has the enzyme of separation, biological organism (whole cell, tissue or organoid etc.), and the various specific enzymess that wherein exist in the whole cell of plant and the various important reaction of their catalysis have given the whole cell of plant huge bio-transformation potentiality.Contain many stereoselective enzymes that have in the whole cell of plant; prepare S-configuration aromatic alcohol with plant intact cell catalysis asymmetric reduction prochirality aromatic ketone; not only can save numerous and diverse enzyme separates and purification step; and the carbon source that only needs to add cheapness in catalytic reaction process just can make cell regeneration go out the required expensive coenzyme of catalytic asymmetric reduction; all enzymes and coenzyme are protected in the natural cellular environment simultaneously, are conducive to the carrying out of bioconversion reaction.Adopt the whole cell of plant carry out bio-transformation be a kind of directly, efficient method, have that plant origin is abundant, cost is low, efficient is high and the product enantio-selectivity is good and the advantage such as reaction process environmental friendliness.
The existing research report of the application of the whole cell of plant in the carbonyl asymmetric reduction reaction.But having a general problem is exactly that the substrate capacity is little, and the enantiomeric excess value of its transformation efficiency and product all has obvious decline when concentration of substrate is slightly high.People (the J Ind Microbiol Biotechnol such as Zhong-Hua Yang, 2008,35:1047-1051) the synthetic corresponding chiral alcohol of the whole cell asymmetric reduction of the plant prochiral ketones of report, the result shows that working as concentration of substrate is 10mmol/L, productive rate only is 28～78%, and enantiomeric excess value is 70～95%.Xiang Liu etc. (Chin Chem Lett, 2010,21:305-308) concentration of substrate with carrot cell and celery cell asymmetric reduction of report also only has 30mmol/L, and the transformation efficiency of most of substrate is between 10%～60%.Therefore in system, add a certain amount of additive that can reduce substrate and product toxicity, should be able to improve the transformation efficiency of substrate and the enantiomeric excess value of product.
Cyclodextrin is the oligose irreducibility series of compounds with the hydrophobic conical structure of ring-type that connects with α-Isosorbide-5-Nitrae-glycosidic link from 6 above D-glucopyranose units that starch obtains.In this cyclodextrin series, the alpha-cylodextrin that is formed by 6 D-glucopyranose units, 7 beta-cyclodextrins that the D-glucopyranose units forms, 8 γ-cyclodextrins that the D-glucopyranose units forms, in addition derivative such as hydroxypropyl-beta-cyclodextrin, the hydroxyethyl-β-cyclodextrin etc. of these cyclodextrin.Because cyclodextrin outside hydrophilic and inner chamber is hydrophobic, thereby it can provide a hydrophobic combining site as enzyme, as the various suitable objects of main body inclusion, such as organic molecule, mineral ion etc.The effect of this optionally inclusion is usually said molecular recognition, consequently forms host-guest complex.Cyclodextrin can improve the solubleness of inclusion complex in water, constructs the solid geometry relation, forms special chirality site, strengthens the stereoselectivity to substrate.The existing patent application of cyclodextrin aspect bio-transformation, the Chinese patent (application number 200710056952.5) " a kind of biological sterol transforming process and application thereof that utilizes cyclodextrin " of University Of Science and Technology Of Tianjin's application, transformation period and transformation efficiency during mainly for the sterol bio-transformation do not relate to stereoselective problem.
Because the outstanding advantage of plant intact cell catalysis asymmetric reduction aspect, in addition, cyclodextrin can improve the solubleness of substrate in water, strengthen the stereoselectivity to substrate by the inclusion effect.Therefore, it will be a brand-new synthetic method that cyclodextrin is got involved catalytic asymmetric reduction aromatic ketone synthesis of chiral intermediate S-configuration aromatic alcohol, can appropriateness solve the low defective of concentration of substrate in the general bio-transformation asymmetric reduction process, can also improve stereoselectivity simultaneously.
Summary of the invention
Purpose of the present invention: provide a kind of cyclodextrin to get involved the method for the synthetic S-configuration aromatic alcohol of plant intact cell catalysis asymmetric reduction aromatic ketone, utilize this special construction of cyclodextrin, cyclodextrin is added in the bio-transformation system of plant intact cell catalysis asymmetric reduction aromatic ketone, select different cyclodextrin for different substrates, and by the molar ratio between regulation and control substrate and the cyclodextrin, improve the transformation efficiency of substrate aromatic ketone and the enantiomeric excess value of product S-configuration aromatic alcohol.
Technical scheme of the present invention: a kind of cyclodextrin is got involved the method for the synthetic S-configuration aromatic alcohol of catalytic asymmetric reduction prochirality aromatic ketone, prepare at plant intact cell catalysis asymmetric reduction aromatic ketone and to add an amount of cyclodextrin in the system of S-structure aromatic alcohol, the whole cell of plant can be selected stem of celery cell, Carrot Roots cell, potato cell or Jerusalem artichoke root cells, and cyclodextrin can be selected beta-cyclodextrin, γ-cyclodextrin, hydroxypropyl-beta-cyclodextrin or hydroxyethyl-β-cyclodextrin.Step is:
(1) the whole cell activation of plant: be in the phosphate buffer soln of concentration 0.1mol/L, pH 5.0～7.0 at reaction medium, add the whole cell of plant and the glucose smashed to pieces, the add-on of the whole cell of plant and glucose is respectively 100～200g/L and 20～40g/L, is that 28～36 ℃, hunting speed are to activate 10～30min under the 120r/min condition in activation temperature;
(2) asymmetric reduction process: add aromatic ketone and cyclodextrin in the system after activation, making substrate aromatic ketone concentration is that the mol ratio of 60mmol/L, substrate aromatic ketone and cyclodextrin is 12: 1～4: 1, be that 28～36 ℃, hunting speed are under the 120r/min condition in temperature of reaction, carry out the bioconversion reaction of catalytic asymmetric reduction aromatic ketone, reaction 10h;
(3) add the whole cell of plant: behind the reaction 10h, add the whole cell of plant and glucose in reaction system, the whole cell of plant and glucose add-on are respectively 100g/L and 20g/L, continue under the same conditions reaction, and total reaction time is 20～36h;
(4) separation detection: after reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), extraction liquid drying, concentrated rear a certain amount of internal standard substance tridecane that adds, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed again, calculate the enantiomeric excess value of substrate conversion efficiency and product.
Beneficial effect of the present invention: the present invention adds cyclodextrin in the bio-transformation system of plant intact cell catalysis asymmetric reduction aromatic ketone, utilize cyclodextrin and substrate aromatic ketone to form inclusion complex, improve the whole enchylema catalytic efficiency of plant, and increase stereoselectivity to substrate, and then improve the transformation efficiency of substrate aromatic ketone and the enantiomeric excess value of product S-configuration aromatic alcohol.The present invention can make the concentration of substrate improve more than 1 times, and the transformation efficiency of substrate can improve more than 20% simultaneously, and the amplification of the enantiomeric excess value of product S-type aromatic alcohol also surpasses 20%.Utilize the present invention at concentration of substrate during for 60mmol/L, the cyclodextrin consumption selects different mol ratios to add according to different substrates, this moment, the transformation efficiency of substrate aromatic ketone was 57～95%, and the enantiomeric excess value of product S-type aromatic alcohol is 85～99%, has higher actual application value.
Embodiment
Following embodiment can make those skilled in the art comprehensively understand the present invention, but does not limit the present invention in any way.
Embodiment 1: the stem of celery cell and the 3g glucose that add 100mL phosphate buffered saline buffer (0.1mol/L, pH6.2), 15g chopping in an Erlenmeyer flask, (120r/min) 15min vibrates in the constant temperature water bath shaker under 32 ℃ of conditions, make the stem of celery cell activation, then add 1mmol beta-cyclodextrin and 6mmol (60mmol/L) methyl phenyl ketone, under uniform temp and hunting speed, react 10h, then in reaction system, add the whole cell of 10g plant and 2g glucose, continue reaction, total reaction time is 28h.After reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), extraction liquid drying, concentrated rear a certain amount of internal standard substance tridecane that adds, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed, the enantiomeric excess value of the transformation efficiency of substrate methyl phenyl ketone and product S-1-phenylethyl alcohol is respectively 95.0% and 96.3% again.
Embodiment 2: the stem of celery cell and the 2g glucose that add 100mL phosphate buffered saline buffer (0.1mol/L, pH5.5), 10g chopping in an Erlenmeyer flask, (120r/min) 10min vibrates in the constant temperature water bath shaker under 30 ℃ of conditions, make the stem of celery cell activation, then add 0.5mmol hydroxypropyl-beta-cyclodextrin and 6mmol (60mmol/L) Propiophenone, under uniform temp and hunting speed, react 10h, then in reaction system, add the whole cell of 10g plant and 2g glucose, continue reaction, total reaction time is 20h.After reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), extraction liquid drying, concentrated rear a certain amount of internal standard substance tridecane that adds, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed, the enantiomeric excess value of the transformation efficiency of substrate Propiophenone and product S-1-phenyl propanol is respectively 75.3% and 88.1% again.
Embodiment 3: adding 100mL phosphate buffered saline buffer (0.1mol/L, pH7.0), 15g smash Carrot Roots cell and 3g glucose to pieces in an Erlenmeyer flask, (120r/min) 10min vibrates in the constant temperature water bath shaker under 30 ℃ of conditions, make the Carrot Roots cell activation, then add 1.5mmol beta-cyclodextrin and 6mmol (60mmol/L) parachloroacetophenone, under uniform temp and hunting speed, react 10h, then in reaction system, add the whole cell of 10g plant and 2g glucose, continue reaction, total reaction time is 32h.After reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), add a certain amount of internal standard substance tridecane after extraction liquid is concentrated, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed, the enantiomeric excess value of the transformation efficiency of substrate parachloroacetophenone and product S-1-rubigan ethanol is respectively 61.9% and 97.4% again.
Embodiment 4: adding 100mL phosphate buffered saline buffer (0.1mol/L, pH6.2), 10g smash Carrot Roots cell and 2g glucose to pieces in an Erlenmeyer flask, (120r/min) 30min vibrates in the constant temperature water bath shaker under 32 ℃ of conditions, make the Carrot Roots cell activation, then add 1.5mmol γ-cyclodextrin and 6mmol (60mmol/L) o-chloroacetophenone, under uniform temp and hunting speed, react 10h, then in reaction system, add the whole cell of 10g plant and 2g glucose, continue reaction, total reaction time is 24h.After reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), add a certain amount of internal standard substance tridecane after extraction liquid is concentrated, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed, the enantiomeric excess value of the transformation efficiency of substrate p-methyl aceto phenone and product S-1-Chloro-O-Phenyl ethanol is respectively 57.1% and 95.8% again.
Embodiment 5: adding 100mL phosphate buffered saline buffer (0.1mol/L, pH6.5), 20g smash Jerusalem artichoke root cells and 4g glucose to pieces in an Erlenmeyer flask, (120r/min) 20min vibrates in the constant temperature water bath shaker under 28 ℃ of conditions, make the activation of Jerusalem artichoke root cells, then add 0.5mmol hydroxypropyl-beta-cyclodextrin and 6mmol (60mmol/L) p-methyl aceto phenone, under uniform temp and hunting speed, react 10h, then in reaction system, add the whole cell of 10g plant and 2g glucose, continue reaction, total reaction time is 28h.After reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), add a certain amount of internal standard substance tridecane after extraction liquid is concentrated, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed, the enantiomeric excess value of the transformation efficiency of substrate p-methyl aceto phenone and product S-1-p-methylphenyl ethanol is respectively 70.4% and 99.0% again.
Embodiment 6: adding 100mL phosphate buffered saline buffer (0.1mol/L, pH6.5), 15g smash Jerusalem artichoke root cells and 3g glucose to pieces in an Erlenmeyer flask, (120r/min) 15min vibrates in the constant temperature water bath shaker under 34 ℃ of conditions, make the activation of Jerusalem artichoke root cells, then add 0.5mmol hydroxyethyl-β-cyclodextrin and 6mmol (60mmol/L) p-methoxy-acetophenone, under uniform temp and hunting speed, react 10h, then in reaction system, add the whole cell of 10g plant and 2g glucose, continue reaction, total reaction time is 32h.After reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), extraction liquid drying, concentrated rear a certain amount of internal standard substance tridecane that adds, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed, the enantiomeric excess value of the transformation efficiency of substrate p-methoxy-acetophenone and product S-1-p-methoxyphenyl ethanol is respectively 63.4% and 98.8% again.
Embodiment 7: adding 100mL phosphate buffered saline buffer (0.1mol/L, pH6.8), 20g smash potato cell and 4g glucose to pieces in an Erlenmeyer flask, (120r/min) 20min vibrates in the constant temperature water bath shaker under 30 ℃ of conditions, make the potato cell activation, then add 1.5mmol hydroxypropyl-beta-cyclodextrin and 6mmol (60mmol/L) m chloroacetophenone, under uniform temp and hunting speed, react 10h, then in reaction system, add the whole cell of 10g plant and 2g glucose, continue reaction, total reaction time is 28h.After reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), extraction liquid drying, concentrated rear a certain amount of internal standard substance tridecane that adds, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed, the enantiomeric excess value of the transformation efficiency of substrate m chloroacetophenone and product S-1-m-chloro phenylethyl alcohol is respectively 60.4% and 95.6% again.
Embodiment 8: adding 100mL phosphate buffered saline buffer (0.1mol/L, pH5.0), 15g smash potato cell and 3g glucose to pieces in an Erlenmeyer flask, (120r/min) 20min vibrates in the constant temperature water bath shaker under 36 ℃ of conditions, make the potato cell activation, then add 1mmol γ-cyclodextrin and 6mmol (60mmol/L) phenyl propyl ketone, under uniform temp and hunting speed, react 10h, then in reaction system, add the whole cell of 10g plant and 2g glucose, continue reaction, total reaction time is 36h.After reaction finishes, filter, filtrate extracts with ethylene dichloride (20mL * 2), extraction liquid drying, concentrated rear a certain amount of internal standard substance tridecane that adds, detect with the gas chromatograph that the CP-Chirosil-DexCB chiral capillary column is housed, the enantiomeric excess value of the transformation efficiency of substrate phenyl propyl ketone and product S-1-phenyl butanols is respectively 66.4% and 85.8% again.
Claims (2)
1. a cyclodextrin is got involved the method that catalytic asymmetric reduction prochirality aromatic ketone synthesizes S-configuration aromatic alcohol, it is characterized in that in the system of the synthetic S-configuration aromatic alcohol of plant intact cell catalysis asymmetric reduction aromatic ketone, adding an amount of cyclodextrin, the whole cell of plant is stem of celery cell, Carrot Roots cell, potato cell or Jerusalem artichoke root cells, cyclodextrin is beta-cyclodextrin, γ-cyclodextrin, hydroxypropyl-beta-cyclodextrin or hydroxyethyl-β-cyclodextrin, and step is as follows:
(1) the whole cell activation of plant: be in the phosphate buffer soln of concentration 0.1mol/L, pH 5.0～7.0 at reaction medium, add the whole cell of plant and the glucose smashed to pieces, the add-on of the whole cell of plant and glucose is respectively 100～200g/L and 20～40g/L, be that 28～36 ℃, hunting speed are under the 120r/min condition in activation temperature, activation 10～30min;
(2) asymmetric reduction process: add aromatic ketone and cyclodextrin in the system after activation, making substrate aromatic ketone concentration is that the mol ratio of 60mmol/L, substrate aromatic ketone and cyclodextrin is 12: 1～4: 1, is that 28～36 ℃, hunting speed are to react 10h under the condition of 120r/min in temperature of reaction;
(3) add the whole cell of plant: behind the reaction 10h, add the whole cell of plant and glucose in reaction system, the whole cell of plant and glucose add-on are respectively 100g/L and 20g/L, continue under the same conditions reaction, and total reaction time is 20～36h;
(4) separation detection: with ethylene dichloride extracting and separating reactant, with the gas chromatograph analyzing and testing gained S-configuration aromatic alcohol that chiral capillary column is housed, calculate the enantiomeric excess value of substrate conversion efficiency and product after reaction finishes.
2. described method according to claim 1, it is characterized in that the substrate aromatic ketone is methyl phenyl ketone, Propiophenone, phenyl propyl ketone, o-chloroacetophenone, m chloroacetophenone, parachloroacetophenone, p-methyl aceto phenone or p-methoxy-acetophenone, product S-configuration aromatic alcohol is S-1-phenylethyl alcohol, S-1-phenyl propanol, S-1-phenyl butanols, S-1-Chloro-O-Phenyl ethanol, S-1-m-chloro phenylethyl alcohol, S-1-rubigan ethanol, S-1-p-methylphenyl ethanol or S-1-p-methoxyphenyl ethanol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109266625A (en) * | 2018-09-28 | 2019-01-25 | 广东食品药品职业学院 | A kind of encoding gene of S type 1- phenylethanol synzyme and its application |
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| CN101240299A (en) * | 2008-03-17 | 2008-08-13 | 江南大学 | Method for preparing optical activity alcohol by using yeast cell to catalytically reduce aromatic ketone |
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| CN109266625A (en) * | 2018-09-28 | 2019-01-25 | 广东食品药品职业学院 | A kind of encoding gene of S type 1- phenylethanol synzyme and its application |
| CN109266625B (en) * | 2018-09-28 | 2021-08-17 | 广东食品药品职业学院 | Coding gene of S-type 1-phenyl ethanol synthetase and application thereof |
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Application publication date: 20130327 |