CN113941365B - Temperature-sensitive catalyst for aromatic ketone asymmetric hydrogen transfer reaction and preparation method thereof - Google Patents
Temperature-sensitive catalyst for aromatic ketone asymmetric hydrogen transfer reaction and preparation method thereof Download PDFInfo
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Abstract
The application belongs to the fields of chiral catalysis and asymmetric synthesis, and discloses a temperature-sensitive catalyst for asymmetric hydrogen transfer reaction of aromatic ketone and a preparation method thereof. The catalyst is prepared by coordination of a chiral temperature-sensitive polymer obtained by copolymerization of acrylamide, acrylonitrile and N-p-styrenesulfonated chiral diamine and a transition metal complex. The catalyst has good and adjustable UCST type temperature sensitivity, the preparation method is simple, and the catalyst has high catalytic activity and enantioselectivity to the asymmetric hydrogen transfer reaction of aromatic ketone, is easy to recycle after the reaction is finished, and has good industrial application prospect.
Description
Technical Field
The application belongs to the fields of chiral catalysis and asymmetric synthesis, and particularly relates to a temperature-sensitive catalyst for asymmetric hydrogen transfer reaction of aromatic ketone and a preparation method thereof.
Background
With the increasing worldwide demand for chiral products, efficient, green production methods of chiral compounds have received general attention. Among various methods for synthesizing chiral compounds, chiral catalysis is the only chiral synthesis method with chiral proliferation effect, is the most effective and practical technology for producing a large amount of chiral compounds, has great application and development values, is more and more focused and valued by people, and becomes the leading-edge research field common to the current catalytic science and organic synthesis science.
Chiral secondary alcohol is an important intermediate for synthesizing bioactive compounds, and has wide application in the fields of pesticides, pharmacy, fine chemical industry, advanced materials and the like. The asymmetric hydrogen transfer reaction of the latent chiral ketone is one of effective ways for synthesizing chiral secondary alcohol, and usually adopts chiral transition metal complex as a catalyst, so that the method has the advantages of mild reaction system conditions, simple operation, low price and easy obtainment of hydrogen sources. However, although homogeneous asymmetric hydrogen transfer has been successful, the problems that chiral metal complex catalysts are difficult to separate and recover after the reaction is finished and products are difficult to purify are not solved well, so that the practical application of the chiral metal complex catalysts is limited to a certain extent. Therefore, the development of the catalyst system which is environment-friendly, efficient, easy to recycle and capable of being recycled for the asymmetric hydrogen transfer reaction of the latent chiral ketone has important research significance and application value.
The temperature-sensitive polymer is a stimulus-responsive high molecular material sensitive to temperature, and can change the solubility of the temperature-sensitive polymer in a solvent according to the change of the temperature of the external environment. The reversible intelligent response behavior enables the temperature-sensitive polymer material to be widely applied in the fields of medicine slow release, biosensing, catalysis and the like. The temperature-sensitive polymer with high critical solution temperature (UCST) has the characteristics of high-temperature dissolution and low-temperature precipitation in water, is used as a carrier for supporting a catalyst, and is helpful for realizing the process of homogeneous catalysis and heterogeneous recovery of the catalyst by changing the temperature of a reaction system, so that great attention is paid to the catalysis field. The application provides a catalyst with UCST type temperature-sensitive property aiming at asymmetric hydrogen transfer reaction of potential chiral ketone.
CN105884968A discloses a preparation method of a temperature-sensitive catalyst for asymmetric hydrogen transfer reaction, which is an early study of the present inventors, and has problems that the temperature of a reaction system needs to be raised to be recovered after the catalytic reaction is finished, and the critical dissolution temperature of the catalyst in an aqueous phase is difficult to adjust, so as to solve the above problems, and the present application is proposed.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide a temperature-sensitive asymmetric hydrogen transfer catalyst which is green, efficient, stable and capable of being recycled and a preparation method thereof.
The preparation method of the temperature-sensitive asymmetric hydrogen transfer catalyst comprises the following steps:
(1) Adding acrylamide, acrylonitrile, an initiator azo-diisobutyronitrile (AIBN), N-p-styrenesulfonated chiral diamine 1 and dimethyl sulfoxide (DMSO) into a reaction vessel, introducing nitrogen, and heating at 50-100 ℃ for reaction for 5-72h. Wherein the mol ratio of the acrylamide to the acrylonitrile is 1:5-20:1, the mol ratio of the acrylamide to the N-p-styrenesulfonation chiral diamine is 1:1-100:1, and the initiator is 0.01-2% of the total amount of the three monomers.
Preferably, the reaction temperature is 50-100 ℃ and the reaction time is 5-72h. More preferably, the reaction temperature is 60-80 ℃ and the reaction time is 24-48h.
Preferably, after the reaction is completed, pouring the reaction solution into a precipitator, filtering and separating precipitate, and vacuum drying to obtain a polymer; preferably, methanol, acetone or diethyl ether is used as precipitant.
(2) The polymer obtained in the step (1) and the transition metal complex ML n And deionized water are added into a reaction vessel to carry out the reaction. Wherein the molar ratio of the metal to the chiral diamine in the polymer is 1:1-1:2
Preferably, the reaction temperature is 20-80 ℃ and the reaction time is 0.5-5h; more preferably, the reaction temperature is 30-60℃and the reaction time is 1-3 hours.
Preferably, after the reaction is completed, the reaction solution is cooled with an ice-water mixture, and the catalyst is obtained by centrifugal separation.
Preferably, the transition metal complex ML n Complexes of ruthenium, rhodium or iridium, including [ RuCl ] 2 (p-cymene)] 2 、(Cp*RhCl 2 ) 2 、(CpRhCl 2 ) 2 、[Rh(COD)Cl] 2 、(Cp*RuCl 2 ) 2 、(CpRuCl 2 ) 2 、(Cp*IrCl 2 ) 2 、(CpIrCl 2 ) 2 、[Ir(COD)Cl] 2 (p-cymene: 4-cymene-base, cp: pentamethyl cyclopentadienyl, cp: cyclopentadienyl, COD:1, 5-cyclooctadienyl).
The reaction formula is:
wherein x: y= (1:5) to (20:1), x: z= (1:1) to (100:1), R 1 ＝R 2 =ph or R 1 -R 2 ＝(CH 2 ) 4 。
The aromatic ketone is acetophenone, monohalogenated acetophenone, dihaloacetophenone, methylacetophenone, methoxyacetophenone, cyanoacetophenone, nitroacetophenone or trifluoromethyl acetophenone.
The application has the following advantages and beneficial effects:
1. the catalyst provided by the application has good and adjustable UCST type temperature sensitivity, has the characteristics of high-temperature dissolution and low-temperature precipitation in aqueous solution, is easy to recycle, and effectively avoids the problem that the homogeneous catalyst is not easy to separate and recycle;
2. the catalyst provided by the application has the advantages of simple preparation method, high catalytic activity and enantioselectivity for asymmetric hydrogen transfer reaction of the latent chiral aromatic ketone, multiple recycling can be realized by utilizing the temperature sensitive property of the catalyst after the reaction is finished, and the product is easy to separate and purify and has good industrial application prospect.
Drawings
FIG. 1 is a plot of turbidity curves for four ruthenium catalysts, where (a) x: y=7:1, x: z=17.5:1, R 1 ＝R 2 ＝Ph，(b)x:y＝6:1、x:z＝17.1:1、R 1 ＝R 2 ＝Ph，(c)x:y＝5:1、x:z＝16.7:1、R 1 ＝R 2 ＝Ph，(d)x:y＝4:1、x:z＝16:1、R 1 ＝R 2 ＝Ph。
Detailed Description
The present application will be described in further detail with reference to specific examples, but the embodiments and the scope of the present application are not limited thereto.
Example 1
Acrylamide (7 mmol), acrylonitrile (1 mmol), and (1S, 2S) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine (0.4 mmol), AIBN (0.08 mmol) and DMSO (5 mL) were added to a round-bottomed flask, stirred and dissolved under nitrogen atmosphere, and then heated to 70℃to react for 24 hours. After the reaction, the reaction solution was poured into 100mL of methanol, and the precipitate was separated by suction filtration, and dried under vacuum at 60℃to obtain a polymer.
The polymer (400 mg) obtained above was reacted with [ RuCl ] 2 (p-cymene)] 2 (0.1 mmol) and deionized water (5 mL) were mixed with stirring, and the mixture was heated to 40℃to react for 3h. And cooling the reaction solution after the reaction is finished, and centrifugally separating to obtain the catalyst.
Example 2
Acrylamide (6 mmol), acrylonitrile (1 mmol), and (1S, 2S) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine (0.35 mmol), AIBN (0.07 mmol) and DMSO (5 mL) were added to a round-bottomed flask, stirred and dissolved under nitrogen atmosphere, and then heated to 70℃to react for 24 hours. After the reaction, the reaction solution was poured into 100mL of methanol, and the precipitate was separated by suction filtration, and dried under vacuum at 60℃to obtain a polymer.
The polymer (400 mg) obtained above was reacted with [ RuCl ] 2 (p-cymene)] 2 (0.1 mmol) and deionized water (5 mL) were mixed with stirring, and the mixture was heated to 40℃to react for 3h. And cooling the reaction solution after the reaction is finished, and centrifugally separating to obtain the catalyst.
Example 3
Acrylamide (5 mmol), acrylonitrile (1 mmol), and (1S, 2S) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine (0.3 mmol), AIBN (0.06 mmol) and DMSO (5 mL) were added to a round-bottomed flask, stirred and dissolved under nitrogen atmosphere, and then heated to 70℃to react for 24 hours. After the reaction, the reaction solution was poured into 100mL of methanol, and the precipitate was separated by suction filtration, and dried under vacuum at 60℃to obtain a polymer.
The polymer (400 mg) obtained above was reacted with [ RuCl ] 2 (p-cymene)] 2 (0.1 mmol) and deionized water (5 mL) were mixed with stirring, and the mixture was heated to 40℃to react for 3h. And cooling the reaction solution after the reaction is finished, and centrifugally separating to obtain the catalyst.
Example 4
Acrylamide (4 mmol), acrylonitrile (1 mmol), and (1S, 2S) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine (0.25 mmol), AIBN (0.05 mmol) and DMSO (5 mL) were added to a round-bottomed flask, stirred and dissolved under nitrogen atmosphere, and then heated to 70℃to react for 24 hours. After the reaction, the reaction solution was poured into 100mL of methanol, and the precipitate was separated by suction filtration, and dried under vacuum at 60℃to obtain a polymer.
The polymer (400 mg) obtained above was reacted with [ RuCl ] 2 (p-cymene)] 2 (0.1 mmol) and deionized water (5 mL) were mixed with stirring, and the mixture was heated to 40℃to react for 3h. And cooling the reaction solution after the reaction is finished, and centrifugally separating to obtain the catalyst.
Example 5
Acrylamide (7 mmol), acrylonitrile (1 mmol), and (1S, 2S) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine (0.4 mmol), AIBN (0.08 mmol) and DMSO (5 mL) were added to a round-bottomed flask, stirred and dissolved under nitrogen atmosphere, and then heated to 70℃to react for 24 hours. After the reaction, the reaction solution was poured into 100mL of methanol, and the precipitate was separated by suction filtration, and dried under vacuum at 60℃to obtain a polymer.
The polymer obtained above (400 mg), (Cp. RhCl) 2 ) 2 (0.1 mmol) and deionized water (5 mL) were mixed with stirring, and the mixture was heated to 40℃to react for 3h. And cooling the reaction solution after the reaction is finished, and centrifugally separating to obtain the catalyst.
Example 6
Acrylamide (7 mmol), acrylonitrile (1 mmol), and (1S, 2S) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine (0.4 mmol), AIBN (0.08 mmol) and DMSO (5 mL) were added to a round-bottomed flask, stirred and dissolved under nitrogen atmosphere, and then heated to 70℃to react for 24 hours. After the reaction, the reaction solution was poured into 100mL of methanol, and the precipitate was separated by suction filtration, and dried under vacuum at 60℃to obtain a polymer.
The polymer obtained above (400 mg)、(Cp*IrCl 2 ) 2 (0.1 mmol) and deionized water (5 mL) were mixed with stirring, and the mixture was heated to 40℃to react for 3h. And cooling the reaction solution after the reaction is finished, and centrifugally separating to obtain the catalyst.
Example 7
Acrylamide (7 mmol), acrylonitrile (1 mmol), and (1S, 2S) -N-p-styrenesulfonylcyclohexamethylenediamine (0.4 mmol), AIBN (0.08 mmol) and DMSO (5 mL) were added to a round-bottomed flask, dissolved by stirring under a nitrogen atmosphere, and then heated to 70℃to react for 24 hours. After the reaction, the reaction solution was poured into 100mL of methanol, and the precipitate was separated by suction filtration, and dried under vacuum at 60℃to obtain a polymer.
The polymer obtained above (400 mg), (Cp. RhCl) 2 ) 2 (0.1 mmol) and deionized water (5 mL) were mixed with stirring, and the mixture was heated to 40℃to react for 3h. And cooling the reaction solution after the reaction is finished, and centrifugally separating to obtain the catalyst.
Example 8
Acrylamide (7 mmol), acrylonitrile (1 mmol), and (1S, 2S) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine (0.4 mmol), AIBN (0.08 mmol) and DMSO (5 mL) were added to a round-bottomed flask, stirred under nitrogen atmosphere to dissolve, and then heated to 80℃to react for 20 hours. After the reaction, the reaction solution was poured into 100mL of methanol, and the precipitate was separated by suction filtration, and dried under vacuum at 60℃to obtain a polymer.
The polymer obtained above (400 mg), (Cp. RhCl) 2 ) 2 (0.1 mmol) and deionized water (5 mL) were mixed with stirring, and the mixture was heated to 40℃to react for 3h. And cooling the reaction solution after the reaction is finished, and centrifugally separating to obtain the catalyst.
Example 9
The catalyst obtained in example 1 (25 mg), acetophenone (1 mmol), sodium formate (5 mmol) and deionized water (2 mL) were placed in a round bottom flask and reacted at 40℃for 4h. After the reaction is finished, cooling the reaction solution by using an ice water bath, and centrifugally separating to obtain a polymer supported ruthenium catalyst and a liquid phase mixture of the reaction. The liquid phase mixture was analyzed by gas chromatograph equipped with chiral capillary column, and the specific results are shown in table 1.
Example 10
The catalyst obtained in example 5 (25 mg), acetophenone (1 mmol), sodium formate (5 mmol) and deionized water (2 mL) were placed in a round bottom flask and reacted at 40℃for 4h. After the reaction is finished, cooling the reaction solution by using an ice water bath, and centrifugally separating to obtain a rhodium catalyst loaded by the polymer and a liquid phase mixture of the reaction. The liquid phase mixture was analyzed by gas chromatograph equipped with chiral capillary column, and the specific results are shown in table 1.
Example 11
The catalyst obtained in example 6 (25 mg), acetophenone (1 mmol), sodium formate (5 mmol) and deionized water (2 mL) were placed in a round bottom flask and reacted at 40℃for 4h. After the reaction is finished, cooling the reaction solution by using an ice water bath, and centrifugally separating to obtain the polymer supported iridium catalyst and a liquid phase mixture of the reaction. The liquid phase mixture was analyzed by gas chromatograph equipped with chiral capillary column, and the specific results are shown in table 1.
Example 12
The catalyst obtained in example 7 (25 mg), acetophenone (1 mmol), sodium formate (5 mmol) and deionized water (2 mL) were placed in a round bottom flask and reacted at 40℃for 4h. After the reaction is finished, cooling the reaction solution by using an ice water bath, and centrifugally separating to obtain a rhodium catalyst loaded by the polymer and a liquid phase mixture of the reaction. The liquid phase mixture was analyzed by gas chromatograph equipped with chiral capillary column, and the specific results are shown in table 1.
Example 13
The catalyst obtained in example 8 (25 mg), acetophenone (1 mmol), sodium formate (5 mmol) and deionized water (2 mL) were placed in a round bottom flask and reacted at 40℃for 4h. After the reaction is finished, cooling the reaction solution by using an ice water bath, and centrifugally separating to obtain a rhodium catalyst loaded by the polymer and a liquid phase mixture of the reaction. The liquid phase mixture was analyzed by gas chromatograph equipped with chiral capillary column, and the specific results are shown in table 1.
TABLE 1 results of asymmetric hydrogen transfer reactions of acetophenone catalyzed by different catalysts
| Examples | Acetophenone conversion (%) | Phenethyl alcohol enantioselectivity (%) |
| 9 | >99 | 94 |
| 10 | >99 | 96 |
| 11 | >99 | 92 |
| 12 | >99 | 96 |
| 13 | >99 | 96 |
As can be seen from Table 1, the polymer supported chiral ruthenium, rhodium and iridium catalysts show high catalytic activity and product enantioselectivity in the acetophenone asymmetric hydrogen transfer reaction, and the two chiral diamine ligands used have equivalent catalytic performance.
Examples 14 to 17
(1) The catalyst obtained in example 5 (25 mg), acetophenone (1 mmol), sodium formate (5 mmol) and deionized water (2 mL) were placed in a round bottom flask and reacted at 40℃for 4h. After the reaction is finished, cooling the reaction solution by using an ice water bath, and centrifugally separating to obtain a rhodium catalyst loaded by the polymer and a liquid phase mixture of the reaction. The liquid phase mixture was subjected to detection analysis by a gas chromatograph equipped with a chiral capillary column.
(2) Washing and drying the rhodium catalyst obtained by centrifugation in the step (1) by acetone and deionized water, and performing catalytic reaction under the same conditions of the step (1) as the catalyst. The cycle was repeated 3 times and the specific results are shown in Table 2.
TABLE 2 stability of temperature-sensitive Polymer-supported rhodium catalysts in acetophenone asymmetric Hydrogen transfer reactions
| Examples | Number of cycles | Acetophenone conversion (%) | Phenethyl alcohol enantioselectivity (%) |
| 14 | 0 | >99 | 96 |
| 15 | 1 | >99 | 96 |
| 16 | 2 | >99 | 95 |
| 17 | 3 | 98 | 95 |
From Table 2, it can be seen that after the chiral rhodium catalyst supported by the polymer is recycled for three times, the conversion rate of acetophenone and the enantioselectivity of the product phenethyl alcohol are basically kept stable, which indicates that the catalyst has good cycle performance and also indicates that the temperature-sensitive property of the catalyst can be effectively utilized for recycling.
The foregoing is merely a preferred embodiment of the present application, and it should be noted that it will be apparent to those skilled in the art that variations and modifications can be made without departing from the scope of the application.
Claims (8)
1. A temperature-sensitive catalyst for asymmetric hydrogen transfer reaction of aromatic ketone is characterized in that: the catalyst is obtained by coordination of a copolymer of acrylamide, acrylonitrile and N-p-styrenesulfonated chiral diamine and a transition metal complex;
the structural general formula of the copolymer of the acrylamide, the acrylonitrile and the N-p-styrenesulfonated chiral diamine is as follows:
wherein x: y= (1:5) to (20:1), x: z= (1:1) to (100:1), R 1 ＝R 2 =ph or R 1 -R 2 ＝(CH 2 ) 4 ；
The transition metal complex is [ RuCl ] 2 (p-cymene)] 2 、(Cp*RhCl 2 ) 2 、(CpRhCl 2 ) 2 、[Rh(COD)Cl] 2 、(Cp*RuCl 2 ) 2 、(CpRuCl 2 ) 2 、(Cp*IrCl 2 ) 2 、(CpIrCl 2 ) 2 、[Ir(COD)Cl] 2 One of them.
2. The temperature-sensitive catalyst for asymmetric hydrogen transfer reaction of aromatic ketone according to claim 1, wherein: the aromatic ketone is acetophenone, monohalogenated acetophenone, dihaloacetophenone, methylacetophenone, methoxyacetophenone, cyanoacetophenone, nitroacetophenone or trifluoromethyl acetophenone.
3. The method for preparing the temperature-sensitive catalyst for asymmetric hydrogen transfer reaction of aromatic ketone according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) Adding acrylamide, acrylonitrile, N-p-styrenesulfonated chiral diamine and an initiator into a reaction solvent, stirring and dissolving the mixture under the nitrogen atmosphere, and then heating the mixture to perform polymerization reaction, wherein the molar ratio of the acrylamide to the acrylonitrile is 1:5-20:1, the molar ratio of the acrylamide to the N-p-styrenesulfonated chiral diamine is 1:1-100:1, and the using amount of the initiator is 0.01% -2% of the total molar amount of the three monomers; (2) And (3) adding the polymer obtained in the step (1), the transition metal complex and deionized water into a reaction vessel to react, wherein the molar ratio of the metal to chiral diamine in the polymer is 1:1-1:2.
4. A method of preparation according to claim 3, characterized in that: the N-p-styrenesulfonated chiral diamine is one of (1S, 2S) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine, (1R, 2R) -N-p-styrenesulfonyl-1, 2-diphenylethylenediamine, (1S, 2S) -N-p-styrenesulfonylcyclohexamethylenediamine and (1R, 2R) -N-p-styrenesulfonylcyclohexamethylenediamine.
5. A method of preparation according to claim 3, characterized in that: the initiator is azodiisobutyronitrile, and the reaction solvent is dimethyl sulfoxide.
6. A method of preparation according to claim 3, characterized in that: the polymerization reaction temperature in the step (1) is 50-100 ℃ and the reaction time is 5-72h.
7. A method of preparation according to claim 3, characterized in that: after the reaction in the step (1) is completed, pouring the reaction liquid into a precipitator, separating to obtain a precipitate, and drying to obtain the polymer.
8. A method of preparation according to claim 3, characterized in that: the reaction temperature of the step (2) is 20-80 ℃ and the reaction time is 0.5-5h; after the reaction is completed, the reaction solution is cooled and centrifugally separated to obtain the catalyst.
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