CN112044472B - Chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst and preparation method thereof - Google Patents
Chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst and preparation method thereof Download PDFInfo
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 87
- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 58
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 56
- 239000011982 enantioselective catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 239000007810 chemical reaction solvent Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007336 electrophilic substitution reaction Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- ZGUNAGUHMKGQNY-ZETCQYMHSA-N L-alpha-phenylglycine zwitterion Chemical compound OC(=O)[C@@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-ZETCQYMHSA-N 0.000 claims description 3
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 3
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 3
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 3
- XSRWPJFTHDOKTA-UHFFFAOYSA-M [Rh]Cl.C1CC=CCCC=C1 Chemical class [Rh]Cl.C1CC=CCCC=C1 XSRWPJFTHDOKTA-UHFFFAOYSA-M 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- MSIFHGPIEOZWQZ-UHFFFAOYSA-N 3-chlorobicyclo[2.2.1]hepta-1,3-diene;rhodium Chemical class [Rh].C1CC2=CC(Cl)=C1C2 MSIFHGPIEOZWQZ-UHFFFAOYSA-N 0.000 claims description 2
- NWBUFJZQWAXFGH-UHFFFAOYSA-K [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1.C1=CCCC=CCC1 Chemical compound [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1.C1=CCCC=CCC1 NWBUFJZQWAXFGH-UHFFFAOYSA-K 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229940079593 drug Drugs 0.000 abstract description 13
- 239000003814 drug Substances 0.000 abstract description 13
- 239000000575 pesticide Substances 0.000 abstract description 5
- 238000011914 asymmetric synthesis Methods 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000003275 alpha amino acid group Chemical group 0.000 abstract 2
- 229940024606 amino acid Drugs 0.000 description 51
- 239000000047 product Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 150000003862 amino acid derivatives Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003821 enantio-separation Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
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- 238000001308 synthesis method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- PIAOLBVUVDXHHL-VOTSOKGWSA-N β-nitrostyrene Chemical compound [O-][N+](=O)\C=C\C1=CC=CC=C1 PIAOLBVUVDXHHL-VOTSOKGWSA-N 0.000 description 2
- -1 1, 4-dichlorobenzyl Chemical group 0.000 description 1
- QDGAVODICPCDMU-UHFFFAOYSA-N 2-amino-3-[3-[bis(2-chloroethyl)amino]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(N(CCCl)CCCl)=C1 QDGAVODICPCDMU-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 238000009509 drug development Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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Abstract
The invention provides a chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst and a preparation method thereof, wherein a catalyst carrier is a chiral mesoporous amino acid polymer with chiral amino acid functional groups; the transition metal is loaded on the surface of the mesoporous amino acid polymer through coordination with an amino acid functional group; the chiral mesoporous amino acid polymer with a cross-linked structure is synthesized by taking cheap and easily-obtained optically active amino acid or derivatives thereof as raw materials, and the transition metal catalyst is loaded on the surface of the polymer. The catalyst can be applied to the fields of asymmetric synthesis, chiral drugs, pesticides and the like, and the production cost of the related fields is reduced.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst and a preparation method thereof, belonging to the fields of porous materials, catalysts and asymmetric catalysis.
Background
Chiral drugs with asymmetric molecular structures are a class of rapidly developing drugs, and due to the complex chiral environment of the human body, chiral drugs often have excellent curative effects, and nearly 40% of the commonly used synthetic drugs in the world are chiral drugs. Chiral drug development is the leading topic of international pharmaceutical research, and usually chiral compounds coexist with their enantiomers in the form of racemic mixtures, however, only one enantiomer has therapeutic effect, and the other enantiomer has no therapeutic effect or even toxic side effects. Therefore, in order to ensure the curative effect and the safety of the chiral drug, the chiral drug has extremely high requirements on the optical purity.
The chiral catalytic synthesis is a technology for directly obtaining an optical pure chiral compound, and the chiral compound with high optical purity can be directly obtained by using an asymmetric structure catalyst to directly catalyze a synthesis reaction. However, the technology also has some disadvantages to be overcome, and most of the currently commonly used asymmetric catalysts are small molecule asymmetric catalysts synthesized by coordination of a transition metal and a chiral ligand, which use chiral molecules which are expensive and difficult to obtain as ligands, and are mostly noble metal complexes which are expensive and difficult to recover. Therefore, the preparation of a cheap, efficient and easily-recycled asymmetric catalyst is a key problem to be solved urgently in chiral catalytic synthesis.
Amino acids are chiral compounds widely existing in nature and are the cheapest class of chiral molecules. The amino and carboxyl functional groups have excellent modifiability and coordination capacity, and can form a stable bidentate complex by being coordinated with metal. Therefore, the method for preparing the chiral catalyst by using the amino acid as the catalyst carrier is a way for obtaining the optical pure chiral compound at low cost. Meanwhile, the mesoporous polymer is a porous material with a large specific surface area, and is widely applied to the fields of catalysis, adsorption, sensing and the like. The catalyst carrier can improve the catalytic efficiency and realize the recycling of the catalyst.
Disclosure of Invention
The invention aims to overcome the problems of difficult synthesis, high price and difficult recovery of the traditional transition metal asymmetric catalyst, and provides a cheap, high-efficiency, recyclable and high-enantioselectivity chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst and a preparation method thereof, which can reduce the production cost of chiral synthesis, chiral drugs and other related fields.
The purpose of the invention is realized by the following steps:
a chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst is characterized in that a catalyst carrier is a chiral mesoporous amino acid polymer with a chiral amino acid functional group; the transition metal is loaded on the surface of the mesoporous amino acid polymer through coordination with an amino acid functional group, and the molecular formula is as follows:
A preparation method of a chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst comprises the following steps:
synthesizing a chiral mesoporous amino acid polymer through electrophilic substitution reaction between a cross-linking agent and amino acid or amino acid derivatives with aromatic groups;
loading a transition metal catalyst on the surface of the chiral mesoporous amino acid polymer through coordination to prepare a chiral mesoporous amino acid polymer loaded transition metal asymmetric catalyst;
the invention also includes such features:
1. the step (1) is specifically as follows: under nitrogen atmosphere, adding amino acid or amino acid derivative with aromatic group, cross-linking agent and cross-linking catalyst into a reaction bottle, and then adding a proper amount of reaction solvent; placing the reaction bottle containing the reactants in an oil bath pan for reaction; after the reaction is finished, cooling to room temperature, filtering out solid matters obtained by the reaction, and putting the solid matters into a Soxhlet extractor to be extracted for 24-96 hours by using methanol; drying the solid in an oven at 30 ℃ to constant weight to obtain a chiral mesoporous amino acid polymer;
2. the step (2) is specifically as follows: adding the chiral mesoporous amino acid polymer, a transition metal catalyst and potassium hydroxide into a reaction bottle in a nitrogen atmosphere, and then adding a proper amount of reaction solvent into the reaction bottle; placing the reaction bottle on a magnetic stirrer to react for 4-16 hours at normal temperature; after the reaction is finished, filtering out solid substances obtained by the reaction, repeatedly washing the product by using a proper amount of methanol, and drying to obtain the mesoporous amino acid polymer loaded transition metal asymmetric catalyst;
3. the mol ratio of the amino acid or the amino acid derivative with the aromatic group, the cross-linking agent and the cross-linking catalyst is 1/0.5-2/0.5-3; the amino acid or amino acid derivative with aromatic group is one or more of optically pure phenylalanine, phenylglycine, tryptophan and aromatic derivative of amino acid; the cross-linking agent is one or more of 1, 4-dichlorobenzyl, biphenyl dichlorobenzyl and dimethoxymethane; the crosslinking catalyst is one of ferric trichloride, aluminum trichloride, concentrated sulfuric acid and concentrated phosphoric acid; the reaction solvent is: the solvent-free solvent is one of 1, 2-dichloroethane, dimethyl sulfoxide and nitromethane; the proportion of the consumption of the reaction solvent to the reactant is 5-50 mL/g; the reaction temperature is between room temperature and 100 ℃; the reaction time is 2-48 hours;
4. the mass ratio of the chiral mesoporous amino acid polymer to the transition metal catalyst to the potassium hydroxide is 4/1-1.2/0.5-0.7; the transition metal catalyst is one of (1, 5-cyclooctadiene) chlororhodium (I) dimer, chloronorbornadiene rhodium dimer, bis (1, 5-cyclooctadiene) iridium chloride (I) dimer, and (cyclooctyl-1, 5-diene) ruthenium dichloride; the reaction solvent is: methanol or ethanol; the reaction time is 12-16 hours.
The chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst has potential application prospects in the fields of asymmetric catalysis, medicines, pesticides and the like. The asymmetric catalyst has the characteristics of low cost, high catalytic efficiency, high enantioselectivity, easy recovery and reusability. And the catalyst synthesis method is simple and easy to operate, the reaction condition is mild, and the post-treatment is convenient. The invention provides a new design and synthesis idea for the synthesis of the novel asymmetric catalyst.
The chiral mesoporous amino acid polymer with a cross-linked structure is synthesized through electrophilic substitution reaction between optically active amino acid or derivatives thereof and a cross-linking agent, and then a transition metal catalyst is loaded on the surface of the chiral mesoporous amino acid polymer, so that the chiral mesoporous amino acid polymer loaded transition metal asymmetric catalyst is prepared and is applied to catalysis of asymmetric reaction. The novel asymmetric catalyst has high enantioselectivity, low cost and simple synthesis, and can be applied to the fields of asymmetric synthesis, chiral drugs, pesticides and the like.
Compared with the prior art, the invention has the beneficial effects that:
the present invention synthesizes the present micromolecule chiral transition metal catalyst which is a complex of transition metal elements and chiral ligands. Chiral ligands of the catalyst are usually difficult to obtain and expensive, and transition metal elements, particularly noble metal elements with excellent catalytic effect, are expensive; and the small molecular catalysts are difficult to recover and have higher use cost. The chiral mesoporous amino acid polymer with a cross-linked structure is synthesized by taking cheap and easily-obtained optically active amino acid or derivatives thereof as raw materials, and the transition metal catalyst is loaded on the surface of the polymer. The catalyst can be applied to the fields of asymmetric synthesis, chiral medicines, pesticides and the like, and the production cost of the related fields is reduced.
Drawings
FIG. 1 is a scanning electron microscope image of a chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst obtained in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst obtained in example 1 of the present invention;
FIG. 3 is an X-ray photoelectron spectrum of a chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst obtained in example 1 of the present invention;
FIG. 4 is a diagram illustrating the distribution of the pore diameters of the chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst obtained in example 1 of the present invention;
FIG. 5 is a chromatogram of a hydrosilylation reaction product catalyzed by a chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention relates to the fields of porous materials, catalysts and asymmetric catalysis, mainly relates to a novel chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst, and particularly relates to synthesis of the novel chiral mesoporous amino acid polymer, support of transition metals on the surface of the novel chiral mesoporous amino acid polymer and asymmetric reaction catalyzed by the catalyst.
Example 1:
1. synthesizing a chiral mesoporous amino acid polymer: 2.0 g of L-phenylalanine, 5.8 g of ferric trichloride and 3.0 g of biphenyl dichlorobenzyl are weighed at normal temperature and normal pressure and put into a three-mouth reaction bottle, and 150 ml of 1, 2-dichloroethane is added after 3 times of nitrogen replacement. The reaction flask is put in an oil bath, slowly heated to 80 ℃, and stirred for reaction for 20 hours. After the reaction was stopped, it was cooled to room temperature. After filtering off the solids, the solids were washed with methanol until the effluent was essentially colorless. The solids were then placed in a soxhlet extractor and extracted with methanol for 96 hours. And taking out the product, washing the product for 2 to 3 times by using absolute ethyl alcohol, and drying the product in vacuum at the temperature of 30 ℃ to constant weight. Yield: 90 percent; the pore diameter and the specific surface area of the chiral mesoporous amino acid polymer are respectively 858 square meters per gram and 4 nanometers through a nitrogen adsorption experiment.
2, transition metal loading: under the nitrogen atmosphere, 42 mg of chiral mesoporous amino acid polymer, 13 mg of (1, 5-cyclooctadiene) chlororhodium (I) dimer and 7.2 mg of potassium hydroxide are sequentially added into a reaction bottle, then 2 ml of methanol is added for reaction at room temperature for 12 hours, after the reaction is finished, a product is filtered out and washed by a proper amount of anhydrous methanol for 4-5 times, and then the product is dried in vacuum to constant weight. Yield: and 93 percent. The pore diameter and the specific surface area of the chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst are respectively 553.1 square meters per gram and 5 nanometers through a nitrogen adsorption experiment.
3. The catalyst synthesized above is used to catalyze the asymmetric hydrosilation reaction of diphenylsilane and styrene. Under the atmosphere of nitrogen, 10.0 mg of chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst, 6.0 ml of chloroform, 0.1 ml of diphenylsilane and 52 mg of styrene are sequentially added into a reactor and uniformly shaken. And (4) after sealing, reacting for 12 hours at 25 ℃, and filtering and recovering the catalyst after the reaction is finished. The product was isolated and purified using silica gel column chromatography with n-hexane/isopropanol =9/1 (volume ratio). After the product was concentrated using a rotary evaporator, it was dried in vacuum at 30 ℃ in a vacuum oven to constant weight. Yield: 90 percent.
4. The enantiomeric excess percentage of the product was tested. The enantiomeric excess percentage of the product was analyzed by high performance liquid chromatography using OX-H chiral chromatography column with n-hexane/isopropanol =99.4/0.6 volume ratio as mobile phase and 0.6 ml/min flow rate. The test results are: the product enantiomeric excess percentage =98%.
Example 2:
1. the catalyst synthesized above is used to catalyze the asymmetric hydrosilation reaction of diphenylsilane and trans-beta-nitrostyrene. Under the atmosphere of nitrogen, 10.0 mg of chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst, 6.0 ml of chloroform, 0.1 ml of diphenylsilane and 74 mg of trans-beta-nitrostyrene are sequentially added into a reactor and shaken up. And (4) after sealing, reacting for 12 hours at 25 ℃, and filtering and recovering the catalyst after the reaction is finished. The product was isolated and purified using silica gel column chromatography with n-hexane/isopropanol =9/1 (volume ratio). After the product was concentrated using a rotary evaporator, it was dried in vacuum at 30 ℃ in a vacuum oven to constant weight. Yield: 83 percent.
2. The enantiomeric excess percentage of the product was tested. The enantiomeric excess percentage of the product was analyzed by high performance liquid chromatography using OX-H chiral chromatography column with n-hexane/isopropanol =99.4/0.6 volume ratio as mobile phase and 0.6 ml/min flow rate. The test results are: the product enantiomeric excess percentage =99%.
Example 3:
1. the catalyst synthesized above is used to catalyze the asymmetric hydrosilation reaction of diphenylsilane and tetravinylpyridine. Under the atmosphere of nitrogen, 10.0 mg of chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst, 6.0 ml of chloroform, 0.1 ml of diphenylsilane and 52.3 mg of tetravinyl pyridine are sequentially added into a reactor, uniformly shaken and sealed, then reacted for 12 hours at 25 ℃, and the catalyst is filtered and recovered after the reaction is finished. The product was isolated and purified by silica gel column chromatography using n-hexane/isopropanol =9/1 (volume ratio). After the product was concentrated using a rotary evaporator, the product was vacuum dried to constant weight in a vacuum oven at 30 degrees celsius. Yield: 85 percent
2. The enantiomeric excess percentage of the product was tested. The enantiomeric excess percentage of the product was analyzed by high performance liquid chromatography using OX-H chiral chromatography column with n-hexane/isopropanol =99.4/0.6 volume ratio as mobile phase and 0.6 ml/min flow rate. The test results are as follows: the product enantiomeric excess percentage =91%.
In summary, the following steps: the invention provides a novel chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst and a synthesis method thereof. The chiral mesoporous amino acid polymer is directly synthesized by electrophilic substitution reaction of optically active amino acid or amino acid derivatives with aromatic groups and a cross-linking agent. Then, the transition metal is loaded on the prepared chiral mesoporous amino acid polymer to prepare a novel chiral mesoporous amino acid polymer loaded transition metal asymmetric catalyst, and the novel chiral mesoporous amino acid polymer loaded transition metal asymmetric catalyst is applied to asymmetric reaction catalysis. The chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst takes the optically active amino acid with aromatic group and derivatives with low cost and wide sources as raw materials, and has the advantages of simple synthesis and preparation method and mild reaction conditions. The novel asymmetric catalyst is applied to asymmetric reaction catalysis, has the characteristics of high reaction yield and high enantioselectivity, has good recoverability and cyclic usability, and has wide application value in the fields of asymmetric synthesis, medicines, pesticides and the like.
Claims (4)
1. A chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst is characterized in that a catalyst carrier is a chiral mesoporous amino acid polymer with chiral amino acid functional groups; the transition metal is loaded on the surface of the mesoporous amino acid polymer through coordination with an amino acid functional group;
the preparation method of the catalyst comprises the following steps:
synthesizing a chiral mesoporous amino acid polymer by an electrophilic substitution reaction between a cross-linking agent catalyzed by a catalyst and amino acid with an aromatic group in a solvent;
the method specifically comprises the following steps: under the nitrogen atmosphere, adding amino acid with aromatic group, cross-linking agent and cross-linking catalyst into a reaction bottle, and then adding a proper amount of reaction solvent; placing the reaction bottle containing the reactants in an oil bath pan for reaction; after the reaction is finished, cooling to room temperature, filtering out solid matters obtained by the reaction, and putting the solid matters into a Soxhlet extractor to be extracted for 24-96 hours by using methanol; drying the solid matter in an oven at 30 ℃ to constant weight to prepare the chiral mesoporous amino acid polymer;
loading a transition metal catalyst on the surface of a chiral mesoporous amino acid polymer through coordination to prepare a chiral mesoporous amino acid polymer loaded transition metal asymmetric catalyst;
the method specifically comprises the following steps: adding the chiral mesoporous amino acid polymer, a transition metal catalyst and potassium hydroxide into a reaction bottle under the nitrogen atmosphere, and then adding a proper amount of reaction solvent into the reaction bottle; placing the reaction bottle on a magnetic stirrer to react for 4-16 hours at normal temperature; and after the reaction is finished, filtering out solid substances obtained by the reaction, repeatedly washing the product by using a proper amount of methanol, and drying to obtain the mesoporous amino acid polymer supported transition metal asymmetric catalyst, wherein the amino acid with aromatic groups is one or more of optically pure phenylalanine, phenylglycine and tryptophan.
2. The method for preparing the chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst according to claim 1, comprising the following steps:
step (1), synthesizing a chiral mesoporous amino acid polymer through electrophilic substitution reaction between a cross-linking agent catalyzed by a catalyst and amino acid with an aromatic group in a solvent;
under the nitrogen atmosphere, adding amino acid with aromatic group, cross-linking agent and cross-linking catalyst into a reaction bottle, and then adding a proper amount of reaction solvent; placing the reaction bottle containing the reactant in an oil bath pan for reaction; after the reaction is finished, cooling to room temperature, filtering out solid matters obtained by the reaction, and putting the solid matters into a Soxhlet extractor to be extracted for 24-96 hours by using methanol; drying the solid matter in an oven at 30 ℃ to constant weight to prepare the chiral mesoporous amino acid polymer;
loading a transition metal catalyst on the surface of the chiral mesoporous amino acid polymer through coordination to prepare a chiral mesoporous amino acid polymer loaded transition metal asymmetric catalyst;
adding the chiral mesoporous amino acid polymer, a transition metal catalyst and potassium hydroxide into a reaction bottle in a nitrogen atmosphere, and then adding a proper amount of reaction solvent into the reaction bottle; placing the reaction bottle on a magnetic stirrer to react for 4-16 hours at normal temperature; after the reaction is finished, filtering out solid substances obtained by the reaction, repeatedly washing the product by using a proper amount of methanol, and drying to obtain the mesoporous amino acid polymer supported transition metal asymmetric catalyst;
the amino acid with aromatic group is one or more of optically pure phenylalanine, phenylglycine and tryptophan.
3. The preparation method of the chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst according to claim 2, wherein the step (1) is characterized in that the molar ratio of the amino acid with an aromatic group, the cross-linking agent and the cross-linking catalyst is 1/0.5 to 2/0.5 to 3; the cross-linking agent is one or more of 1, 4-p-dichlorobenzyl, biphenyl dichlorobenzyl and dimethoxymethane; the crosslinking catalyst is one of ferric trichloride, aluminum trichloride, concentrated sulfuric acid and concentrated phosphoric acid; the reaction solvent is: 1, 2-dichloroethane, dimethyl sulfoxide or nitromethane; the proportion of the using amount of the reaction solvent to the reactant is 5-50 mL/g; the reaction temperature is between room temperature and 100 ℃; the reaction time is 2-48 hours.
4. The method for preparing the chiral mesoporous amino acid polymer supported transition metal asymmetric catalyst according to claim 2, wherein the step (2) is carried out in such a manner that the mass ratio of the chiral mesoporous amino acid polymer to the transition metal catalyst to the potassium hydroxide is 4/1 to 1.2/0.5 to 0.7; the transition metal catalyst is one of (1, 5-cyclooctadiene) chlororhodium (I) dimer, chloronorbornadiene rhodium dimer, bis (1, 5-cyclooctadiene) iridium chloride (I) dimer and (cyclooctyl-1, 5-diene) ruthenium dichloride; the reaction solvent is: methanol or ethanol; the reaction time is 12-16 hours.
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