CN101195096B - Chiral latex catalyst, production method and application thereof - Google Patents
Chiral latex catalyst, production method and application thereof Download PDFInfo
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Abstract
The invention discloses a chiral emulsion catalyst. A chiral catalyst which is composed of ASn and provided with surface activity is dissolved into ketone under indoor temperature, water is added slowly under the condition of fully mixing, and thereby the mixed liquid forms into the chiral emulsion. Under a comparatively temperate condition, an asymmetrical direct aldol reaction between ketone and aldehyde can be catalyzed with high selectivity by the chiral emulsion, and thereby an aldol product with an over 90% enantio selectivity can be obtained. The characteristics of the invention are that a past method that the asymmetrical direct aldol reaction is catalyzed by a organic phase is changed, the chiral emulsion is adopted as the medium of reactions, thereby catalytic reactions can occur on chiral interfaces, both the activity and the selectivity of reactions are increased to a higher degree, and the selectivity of the reactions can reach over 99% in the greatest extent.
Description
Technical field
The present invention relates to a kind of chirality latex catalyst.
The invention still further relates to the preparation method of above-mentioned chirality latex catalyst.
The invention still further relates to of the application of above-mentioned chirality latex catalyst in the asymmetric direct aldol reaction of catalysis.
Background technology
The Aldol reaction refers to the addition reaction of the carbonyls and the aldehyde ketone of enolization, can form a new C-C key in the reaction.The Aldol reaction is one of important methodology of organic synthesis, is widely used among the preparation of many industrial chemicals.Asymmetric aldol is reflected at and forms new C-C key and have two chiral centres to form simultaneously at the most, and the special construction of product beta-hydroxy ketone makes it occupy important status in natural products synthetic.Asymmetric aldol reaction has been widely used in chiral fine chemicals and the medicine production.Develop the popular research topic that asymmetric aldol reacts also to be become in the Synthetic Organic Chemistry.Asymmetric aldol reaction can be divided into two classes substantially: a class is substrate ketone or ester to be derived react for the form of enol; Another kind of is that the direct reaction of aldehyde and ketone is asymmetric direct aldol reaction.The latter does not need to make operation easier the substrate enolization in advance, thereby has caused people's extensive concern in recent years.People such as List in 2000 find the asymmetric direct aldol reaction that simple organic molecule such as L-proline just can catalysis.New era of organic molecule catalysis has been started in people's such as List discovery.Compare with transition-metal catalyst, organic molecule is easy to get, reaction system does not have metal residual, can separate from product and be repeated to utilize, thereby the asymmetric direct aldol reaction of organic molecule catalysis is considered to be the reaction of green economy.But also there are some shortcomings in the List catalyst system and catalyzing, and as catalyst efficiency not high (catalyst amount account for usually reaction substrate about 30%), the ee value of product is generally lower.For this reason, people have carried out a large amount of research to the transformation of L-proline, in the hope of obtaining higher catalytic activity and stereoselectivity.
It seems from the research of having reported, the catalytic activity of the direct aldol of most right titles reaction and optionally improvement all in pure organic phase solution, carry out.Yet, reduce and use or do not use poisonous, the difficult organic reagent that separates to make solvent and adopt new reaction medium imperative in the today of carrying out environmental protection.A kind of reaction medium that emulsion is so just.To be one or more liquid with particulate (drop or liquid crystal) form be dispersed in emulsion constitutes the heterogeneous dispersion with quite stable in another immiscible liquid, and this system issues lactogenesis in the effect of emulsifying agent (great majority are for being made of the surfactant of amphiphilic structure the hydrophilic group lipophilic group) and forms emulsion.One of common emulsion is the water or the aqueous solution (water) mutually, and another is the organic facies (common name oil phase) immiscible with water mutually.When adopting emulsion to be the medium of organic reaction, reaction occurs on water oil interface, contact fully between reaction substrate and the catalyst, thereby reactive activity is improved significantly.When using chirality latex as the medium of asymmetric reaction, except reactive activity is improved, owing to formed orderly asymmetric microenvironment at the interface of profit, the asymmetric reaction of carrying out in this zone has quite high stereoselectivity in addition.And emulsion is thermodynamic unstable system, and under static or centrifugal condition, emulsion is by the breakdown of emulsion layering, and product and catalyst can be very convenient separated, and catalyst can reclaim again and use.
Chirality latex does not appear in the newspapers so far as the patent of the medium of asymmetric organic synthesis.At this, the present invention is a model reaction with asymmetric direct aldol reaction, with this application characteristic and the prospect of chirality latex in asymmetric organic synthesis is described.
Summary of the invention
The object of the present invention is to provide a kind of chirality latex catalyst.
Another purpose of the present invention is to provide the preparation method of above-mentioned chirality latex catalyst.
Characteristics of the present invention are to have changed the way of in the past carrying out the asymmetric direct aldol reaction of catalysis in organic facies, and the employing chirality latex is as the medium of this reaction, thereby catalytic reaction is occurred on the chirality interface, and reactive activity and selectivity have obtained improving significantly.
For achieving the above object, chirality latex catalyst provided by the invention wherein has surface-active chiral catalyst and is dissolved in ketone and the water, and mixed liquor forms chirality latex; The expression formula of chiral catalyst is AS
n, structure as shown in the formula
Wherein, A refers to 4-hydroxy-proline skeleton, S
nRefer to oxyalkyl chain, S
nIn n refer to the number of alkoxyl carbochain carbon atom, the number of this carbochain carbon atom is more than or equal to 6, as C
6H
11O, C
8H
15O, C
10H
19O, C
12H
23O, C
14H
27O, C
16H
31O, C
18H
35O; Preferred C
10H
19O, C
12H
23O, C
18H
35O; Best C
12H
23O.
The method of the above-mentioned chirality latex catalyst of preparation provided by the invention under the room temperature, will consist of AS
nThe surface-active chiral catalyst that has be dissolved in the ketone, stir down and add entry, mix the formation chirality latex catalyst;
The type of chirality latex catalyst is Water-In-Oil, oil-in-water or multiple chirality latex catalyst; Wherein water in the Water-In-Oil chirality latex catalyst and chiral catalyst mass ratio are 1-100, preferred 10-60, best 33; The oil in the oil-in-water chirality latex catalyst and the mass ratio of chiral catalyst are 50-200, preferred 60-150, best 82.
Described preparation method, wherein, ketone is cyclohexanone or cyclopentanone.
Chirality latex catalyst provided by the invention is in the application of the asymmetric direct aldol reaction of catalysis, and its condition is: in air atmosphere, under the room temperature, reaction substrate aldehyde is 7-20, preferred 7-20, best 7 or 14 with the molal weight ratio of chiral catalyst.
Described application, wherein, reaction substrate aldehyde is aromatic aldehyde and fatty aldehyde.
Described application, wherein, reaction substrate aldehyde is benzaldehyde, 4-nitrobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-chloro benzaldehyde, 4-methoxybenzaldehyde, 4-tolyl aldehyde, the fluorine-based benzaldehyde of 4-, 4-bromo benzaldehyde, Furan Aldehydes, pyridine aldehydes, hexahydrobenzaldehyde; Preferred benzaldehyde, 4-nitrobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-chloro benzaldehyde, 4-methoxybenzaldehyde, 4-tolyl aldehyde, the fluorine-based benzaldehyde of 4-, 4-bromo benzaldehyde; Best benzaldehyde, 4-nitrobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-chloro benzaldehyde, 4-methoxybenzaldehyde.
Under relatively mild condition, but the asymmetric direct aldol reaction of chirality latex highly selective catalysis ketone provided by the invention and aldehyde obtains enantioselectivity greater than the aldol product more than 90%.
In the reaction with aldehyde and chiral catalyst AS
nThe molal weight ratio be 7～20, preferred 7～20, best 7 or 14.
Chirality latex of the present invention be stir or ultrasonic condition under form, the type of emulsion is relevant with the consumption of oil-water ratio and surfactant, can be oil-in-water (O/W) and Water-In-Oil (W/O) emulsion.In addition, for the selection of two-phase liquid, except water/oily two-phase, also can fluorine two-phase or other immiscible oil/oily two-phase (for example ionic liquid/oil phase).Under the reaction condition, wherein a form with drop be dispersed in another mutually in, surfactant also is that catalyst is self-assembled on the interface of two-phase, catalytic reaction occurs on the chirality interface, because the high-ratio surface of decentralized photo, between the reaction substrate and reaction substrate with and catalyst between can contact fully, reactive activity increases greatly; Because chiral catalyst has formed orderly asymmetric microenvironment in the self assembly of the interface of profit, the asymmetric reaction of carrying out in this zone has quite high stereoselectivity.And emulsion is thermodynamic unstable system, and under static or centrifugal condition, emulsion is by the breakdown of emulsion layering, and product and catalyst can be easy to separated, and catalyst can reclaim again and use.
The chiral surfaces activating agent also is a catalyst among the present invention, and it is the key that forms emulsion and catalytic reaction.When design has surface-active chiral catalyst, surface-active and catalytic performance organically be combined.The type of selected surfactant can be ionic surfactant, nonionic surface active agent or high molecular surfactant.Catalyst is proline and its derivative, can be other amino acid and derivative thereof, also can be dipeptides or polypeptide.
The present invention is not limited only to asymmetric direct aldol reaction, chirality latex can also be expanded in other asymmetric organic syntheses, for example asymmetric Mannich reaction, asymmetric Michael Reaction, asymmetric α-amido (oxygen) is changed reaction or asymmetric B-H reaction.
Specifically, the preparation of chirality latex of the present invention and the method that is used for the asymmetric direct aldol reaction of catalysis thereof have the following advantages:
1, chiral surfaces activating agent and catalyst can organically combine, promptly on molecular level, according to the hydrophile-lipophile balance of emulsion with and the characteristics of catalystic converter system, the structure of modulation surface-active part partly designs and assembles catalytic activity simultaneously.
2, selected reaction medium is that the type of emulsion can modulation in catalytic reaction, can be oil-in-water, Water-In-Oil, oil bag oil or multiple-phase emulsion.Under the reaction condition, catalytic reaction occurs on the chirality interface, and reactive activity increases greatly; In addition, chiral catalyst has formed orderly asymmetric microenvironment in the self assembly of the interface of profit, and the asymmetric reaction of carrying out in this zone has quite high stereoselectivity.
3, chirality latex is not limited only to can also expand in other asymmetric organic syntheses not to direct aldol reaction, for example asymmetric Mannich reaction, and asymmetric Michael Reaction, asymmetric α-amido (oxygen) is changed reaction or asymmetric B-H reaction.
The specific embodiment
In order to further specify the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1
Catalyst A S
12Preparation, structural formula is as follows:
AS
12
Under the room temperature nitrogen atmosphere, the DMF that in flask at the bottom of the 100ml garden, adds the 30ml drying, add 4-hydroxy-proline (4.45g then successively, 34mmol) Anhydrous potassium carbonate (4.64g, 34mmol) sodium iodide 0.27g 2mmol) with behind this mixed liquor stirring reaction 30min, adds 6.0ml benzyl bromine, continue stirring reaction, spend the night.Reactant liquor decompression concentrates, with 80ml washing, 3 * 60ml ethyl acetate extraction, and water (60ml) successively, saturated aqueous common salt (30ml) is washed, and anhydrous sodium sulfate drying filters, and concentrates back column chromatography (benzinum: ethyl acetate=1: 1).The liquid that obtains is dissolved in the 30ml dry pyridine, is chilled to 0 ℃, stirs to add 4ml dodecyl acyl chlorides down.Stirring at room reaction 5h, decompression concentrates.With 100ml ethyl acetate dilution, water (100ml) successively, saturated aqueous common salt (100ml) is washed, and anhydrous sodium sulfate drying filters, and concentrates back column chromatography (benzinum: ethyl acetate=7: 1).The liquid that obtains is dissolved in the methyl alcohol of 30ml drying, adds 0.3g5%Pd/C, places autoclave, hydrogen exchange 3 times, and in the 10atm hydrogen pressure, 50 ℃ of following stirring reaction 24h filter then, and decompression obtains final products AS after concentrating
12 1H?NMR(400MHz，CDCl
3)δ(ppm)0.79-0.83(t，3H)，1.18-1.21(m，16H)，1.51-1.53(m，2H)，2.30-2.34(m，5H)，3.33-3.66(m，1H)，3.66-3.69(m，1H)，4.25-4.30(m，1H)，5.27(m，1H).
Embodiment 2
Catalyst A S
10Preparation, structural formula is as follows:
AS
10
Under the room temperature nitrogen atmosphere, the DMF that in flask at the bottom of the 100ml garden, adds the 30ml drying, add 4-hydroxy-proline (4.45g then successively, 34mmol) Anhydrous potassium carbonate (4.64g, 34mmol) sodium iodide 0.27g, 2mmol), behind this mixed liquor stirring reaction 30min, add 6.0ml benzyl bromine, continue stirring reaction, spend the night.Reactant liquor decompression concentrates, with 80ml washing, 3 * 60ml ethyl acetate extraction, and water (60ml) successively, saturated aqueous common salt (30ml) is washed, and anhydrous sodium sulfate drying filters, and concentrates back column chromatography (benzinum: ethyl acetate=1: 1).The liquid that obtains is dissolved in the 30ml dry pyridine, is chilled to 0 ℃, stirs to add 3ml certain herbaceous plants with big flowers alkyl acyl chloride down.Stirring at room reaction 5h, decompression concentrates.With 100ml ethyl acetate dilution, water (100ml) successively, saturated aqueous common salt (100ml) is washed, and anhydrous sodium sulfate drying filters, and concentrates back column chromatography (benzinum: ethyl acetate=7: 1).The liquid that obtains is dissolved in the methyl alcohol of 30ml drying, adds 0.3g 5%Pd/C, places autoclave, hydrogen exchange 3 times, and in the 10atm hydrogen pressure, 50 ℃ of following stirring reaction 24h filter then, and decompression obtains final products AS after concentrating
10
Embodiment 3
Catalyst A S
18Preparation, structural formula is as follows:
AS
18
Under the room temperature nitrogen atmosphere, the DMF that in flask at the bottom of the 100ml garden, adds the 30ml drying, add 4-hydroxy-proline (4.45g then successively, 34mmol) Anhydrous potassium carbonate (4.64g, 34mmol) sodium iodide 0.27g, 2mmol), with this mixed liquor stirring reaction 20min, add 6.0ml benzyl bromine, continue stirring reaction, spend the night.Reactant liquor decompression concentrates, with 80ml washing, 3 * 60ml ethyl acetate extraction, and water (60ml) successively, saturated aqueous common salt (30ml) is washed, and anhydrous sodium sulfate drying filters, and concentrates back column chromatography (benzinum: ethyl acetate=1: 1).The liquid that obtains is dissolved in the 30ml dry pyridine, is chilled to 0 ℃, stirs to add the 5ml octadecyl chloride down.Stirring at room reaction 5h, decompression concentrates.With 100ml ethyl acetate dilution, water (100ml) successively, saturated aqueous common salt (100ml) is washed, and anhydrous sodium sulfate drying filters, and concentrates back column chromatography (benzinum: ethyl acetate=7: 1).The liquid that obtains is dissolved in the methyl alcohol of 30ml drying, adds 0.3g 5%Pd/C, places autoclave, hydrogen exchange 3 times, and in the 10atm hydrogen pressure, 50 ℃ of following stirring reaction 24h filter then, and decompression obtains final products AS after concentrating
18
Embodiment 4
In the air atmosphere, under the room temperature, get the 1ml cyclohexanone in reaction tube, add catalyst A S
12(5.8mg, 0.019mmol), vigorous stirring number minute, after treating catalyst dissolution, add the water of 400 μ l, continue vigorous stirring to above-mentioned solution formation milky white emulsion, (37.5mg, 0.25mmol), vigorous stirring is reacted 14h toward wherein adding paranitrobenzaldehyde.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield:＞95%, the de value of product and ee value by high performance liquid chromatography record (Aglient HPLC 1100, Chiralpak AD-H, 254nm, iPr/Hex=20/80,0.5ml/min).Test result is listed in table 1.
Embodiment 5
In the air atmosphere, under the room temperature, get the 0.7ml cyclohexanone in reaction tube, add catalyst A S
12(12mg, 0.038mmol), vigorous stirring number minute, after treating catalyst dissolution, the water that adds 280 μ l, continue vigorous stirring to above-mentioned solution formation Water-In-Oil (W/O) type emulsion, slowly add entry 6.7ml toward above-mentioned emulsion again, this moment, emulsion type changed oil-in-water (O/W) emulsion into.(37.5mg, 0.25mmol), vigorous stirring is reacted 24h to add paranitrobenzaldehyde toward above-mentioned oil-in-water (O/W) emulsion.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield:＞95%, the de value of product and ee value by high performance liquid chromatography record (Aglient HPLC 1100, ChiralpakAD-H, 254nm, iPr/Hex=20/80,0.5ml/min).Test result is listed in table 1.
Embodiment 6
In the air atmosphere, under the room temperature, get the 1ml cyclohexanone in reaction tube, add 5.3mg (0.019mmol) catalyst A S
10, vigorous stirring number minute, treat catalyst dissolution after, add the water of 400 μ l, after continuing vigorous stirring to above-mentioned solution and forming milky white emulsion, toward wherein add paranitrobenzaldehyde (37.5mg, 0.25mmol), vigorous stirring reaction 13h.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield:＞95%, the de value of product and ee value by high performance liquid chromatography record (AglientHPLC 1100, Chiralpak AD-H, 254nm, iPr/Hex=20/80,0.5ml/min).Test result is listed in table 1.
Embodiment 7
In the air atmosphere, under the room temperature, get the 1ml cyclohexanone in reaction tube, add catalyst A S
18(7.4mg, 0.019mmol), vigorous stirring number minute, after treating catalyst dissolution, add the water of 400 μ l, continue vigorous stirring to above-mentioned solution formation milky white emulsion, (37.5mg, 0.25mmol), vigorous stirring is reacted 22h toward wherein adding paranitrobenzaldehyde.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield:＞95%, the de value of product and ee value by high performance liquid chromatography record (Aglient HPLC 1100, Chiralpak AD-H, 254nm, iPr/Hex=20/80,0.5ml/min).Test result is listed in table 1.
Embodiment 8
In the air atmosphere, under the room temperature, get the 1ml cyclohexanone in reaction tube, add catalyst A S
12(12mg, 0.037mmol), vigorous stirring number minute, after treating catalyst dissolution, add the water of 400 μ l, continue vigorous stirring to above-mentioned solution formation milky white emulsion, (37.5mg, 0.25mmol), vigorous stirring is reacted 18h toward wherein adding o-nitrobenzaldehyde.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield: 94%, the de value of product and ee value by high performance liquid chromatography record (Aglient HPLC 1100, Chiralpak OD-H, 254nm, iPr/Hex=5/95,1.0ml/min).Test result is listed in table 1.
Embodiment 9
In the air atmosphere, under the room temperature, get the 1ml cyclohexanone in reaction tube, add catalyst A S
12(12mg, 0.037mmol), vigorous stirring number minute, after treating catalyst dissolution, add the water of 400 μ l, continue vigorous stirring to above-mentioned solution formation milky white emulsion, (37.5mg, 0.25mmol), vigorous stirring is reacted 12h toward wherein adding m-nitrobenzaldehyde.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield:＞95%, the de value of product and ee value by high performance liquid chromatography record (Aglient HPLC 1100, Chiralpak AD-H, 254nm, iPr/Hex=5/95,1.0ml/min).Test result is listed in table 1.
Embodiment 10
In the air atmosphere, under the room temperature, get the 1ml cyclohexanone in reaction tube, add catalyst A S
12(12mg, 0.037mmol), vigorous stirring number minute, treat catalyst dissolution after, add the water of 400 μ l, after continuing vigorous stirring to above-mentioned solution and forming milky white emulsion, toward wherein add to the chloro benzaldehyde (35mg, 0.25mmol), vigorous stirring reaction 38h.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield: 40%, the de value of product and ee value by high performance liquid chromatography record (AglientHPLC 1100, Chiralpak AD-H, 220nm, iPr/Hex=10/90,0.5ml/min).Test result is listed in table 1.
Embodiment 11
In the air atmosphere, under the room temperature, get the 1ml cyclohexanone in reaction tube, add catalyst A S
12(12mg, 0.037mmol), vigorous stirring number minute, after treating catalyst dissolution, add the water of 400 μ l, continue vigorous stirring to above-mentioned solution formation milky white emulsion, (30 μ l, 0.25mmol), vigorous stirring is reacted 70h toward wherein adding P-methoxybenzal-dehyde.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield: 70%, the de value of product and ee value by high performance liquid chromatography record (Aglient HPLC 1100, Chiralpak AD-H, 220nm, iPr/Hex=10/90,0.5ml/min).Test result is listed in table 1.
Embodiment 12
In the air atmosphere, under the room temperature, get the 1ml cyclohexanone in reaction tube, add catalyst A S
12(12mg, 0.037mmol), vigorous stirring number minute, treat catalyst dissolution after, add the water of 400 μ l, after continuing vigorous stirring to above-mentioned solution and forming milky white emulsion, toward wherein add benzaldehyde (27 μ l, 0.25mmol), vigorous stirring reaction 38h.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield: 94%, the de value of product and ee value by high performance liquid chromatography record (Aglient HPLC1100, Chiralpak OD-H, 220nm, iPr/Hex=10/90,1.0ml/min).Test result is listed in table 1.
Embodiment 13
In the air atmosphere, under the room temperature, get the 1ml cyclopentanone in reaction tube, add catalyst A S
12(12mg, 0.037mmol), vigorous stirring number minute, after treating catalyst dissolution, add the water of 400 μ l, continue vigorous stirring to above-mentioned solution formation milky white emulsion, (37.5mg, 0.25mmol), vigorous stirring is reacted 38h toward wherein adding paranitrobenzaldehyde.With the above-mentioned reaction of 5ml saturated ammonium chloride solution cancellation, 3 * 3ml ethyl acetate extraction, merge organic facies with anhydrous magnesium sulfate drying, filter.Rotary evaporation concentrates back column chromatography (benzinum: ethyl acetate=3: 1).Obtain the aldol product.Separation yield:＞95%, the de value of product and ee value by high performance liquid chromatography record (Aglient HPLC 1100, Chiralpak AD-H, 254nm, iPr/tBuOH/Hex=10/10/80,0.5ml/min).Test result is listed in table 1.
Table 1 experimental result
Claims (7)
1. a chirality latex catalyst wherein has surface-active chiral catalyst and is dissolved in ketone and the water, and mixed liquor forms chirality latex; Described ketone is cyclohexanone or cyclopentanone;
The structure of chiral catalyst as shown in the formula
Wherein, n=6,8,10,12,14,16 or 18 in the structural formula.
2. chirality latex catalyst as claimed in claim 1, wherein, n=12.
3. the method for preparing claim 1 or 2 described chirality latex catalysts under the room temperature, has surface-active chiral catalyst and is dissolved in the ketone described, stirs down to add entry, mixes the formation chirality latex catalyst; Described ketone is cyclohexanone or cyclopentanone;
The type of chirality latex catalyst is Water-In-Oil, oil-in-water or multiple chirality latex catalyst; Wherein water in the Water-In-Oil chirality latex catalyst and chiral catalyst mass ratio are 1～100, and the oil in the oil-in-water chirality latex catalyst and the mass ratio of chiral catalyst are 50～200.
4. preparation method as claimed in claim 3, wherein, water and chiral catalyst mass ratio are 33 in the Water-In-Oil chirality latex catalyst, oil is 82 with the mass ratio of chiral catalyst in the oil-in-water chirality latex catalyst.
5. the described chirality latex catalyst of claim 1 is in the application of the asymmetric direct aldol reaction of catalysis, and in air atmosphere, under the room temperature, reaction substrate aldehyde is 7～14 with the molal weight ratio of chiral catalyst.
6. application as claimed in claim 5, wherein, reaction substrate aldehyde is aromatic aldehyde and fatty aldehyde.
7. application as claimed in claim 5, wherein, reaction substrate aldehyde is benzaldehyde, 4-nitrobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-chloro benzaldehyde, 4-methoxybenzaldehyde, 4-tolyl aldehyde, the fluorine-based benzaldehyde of 4-, 4-bromo benzaldehyde, Furan Aldehydes, pyridine aldehydes or hexahydrobenzaldehyde.
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| CN102452971A (en) * | 2010-10-29 | 2012-05-16 | 上海医药工业研究院 | L-hydroxyproline derivative and preparation method thereof |
| CN103372461B (en) * | 2012-04-28 | 2014-12-10 | 中国科学院大连化学物理研究所 | Chiral emulsion catalyst as well as preparation method and application thereof |
| CN106810537B (en) * | 2015-11-27 | 2019-05-07 | 中国科学院大连化学物理研究所 | One kind being suitable for water phase and an oil phase system chiral catalyst and its preparation and application |
Citations (2)
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|---|---|---|---|---|
| WO1994024104A1 (en) * | 1993-04-08 | 1994-10-27 | Oxford Asymmetry Limited | Improvements in or relating to chiral auxiliaries |
| CN1383920A (en) * | 2002-05-16 | 2002-12-11 | 华东师范大学 | L-sulforamidate type chiral ionic liquid and its prepn |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994024104A1 (en) * | 1993-04-08 | 1994-10-27 | Oxford Asymmetry Limited | Improvements in or relating to chiral auxiliaries |
| CN1383920A (en) * | 2002-05-16 | 2002-12-11 | 华东师范大学 | L-sulforamidate type chiral ionic liquid and its prepn |
Non-Patent Citations (1)
| Title |
|---|
| 陈五红等.(4S)-苯氧基-(S)-脯氨酸的合成.《苏州大学学报(自然科学版)》.2004,第20卷(第1期),58-59，67. * |
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