CN115806504B - Asymmetric chiral ligand and preparation method thereof, prepared catalyst, synthesis method and application - Google Patents
Asymmetric chiral ligand and preparation method thereof, prepared catalyst, synthesis method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000003446 ligand Substances 0.000 title claims abstract description 56
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010949 copper Substances 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- NCNGKAPNQHDQBA-UHFFFAOYSA-N methyl 6-chloro-2-hydroxy-3-oxo-1h-indene-2-carboxylate Chemical compound ClC1=CC=C2C(=O)C(C(=O)OC)(O)CC2=C1 NCNGKAPNQHDQBA-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 96
- 238000006243 chemical reaction Methods 0.000 claims description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 150000001879 copper Chemical class 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- STVVMTBJNDTZBF-VIFPVBQESA-N L-phenylalaninol Chemical compound OC[C@@H](N)CC1=CC=CC=C1 STVVMTBJNDTZBF-VIFPVBQESA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000004729 solvothermal method Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 23
- 239000013078 crystal Substances 0.000 description 18
- 239000005907 Indoxacarb Substances 0.000 description 11
- VBCVPMMZEGZULK-NRFANRHFSA-N indoxacarb Chemical compound C([C@@]1(OC2)C(=O)OC)C3=CC(Cl)=CC=C3C1=NN2C(=O)N(C(=O)OC)C1=CC=C(OC(F)(F)F)C=C1 VBCVPMMZEGZULK-NRFANRHFSA-N 0.000 description 11
- 239000012621 metal-organic framework Substances 0.000 description 11
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- 230000008569 process Effects 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- NCNGKAPNQHDQBA-NSHDSACASA-N methyl (2s)-6-chloro-2-hydroxy-3-oxo-1h-indene-2-carboxylate Chemical compound ClC1=CC=C2C(=O)[C@@](C(=O)OC)(O)CC2=C1 NCNGKAPNQHDQBA-NSHDSACASA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical group N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 1
- PVFDJRIEGYDIEK-UHFFFAOYSA-N 3-tert-butyl-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC=C1O PVFDJRIEGYDIEK-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
- 235000021513 Cinchona Nutrition 0.000 description 1
- 241000157855 Cinchona Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 101100109871 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) aro-8 gene Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- HVVNJUAVDAZWCB-YFKPBYRVSA-N [(2s)-pyrrolidin-2-yl]methanol Chemical class OC[C@@H]1CCCN1 HVVNJUAVDAZWCB-YFKPBYRVSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000152 carbamate pesticide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011982 enantioselective catalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an asymmetric chiral ligand, a preparation method, a prepared catalyst, a synthesis method and application thereof, wherein the structural formula of the asymmetric chiral ligand is as followsThe catalyst is prepared by a secondary cooling crystallization method, is simple and time-saving and can be prepared in a large amount; the catalyst unit cell parameters prepared were: the space group is P3 2 ，α＝β＝90°，γ＝120°，Z=3; the catalyst structure has hydrophobic chiral pore canal with the size of 1.03nm and is inlaid with catalytic activity metallic copper sites with high density, so that 5-chloro-1-oxo-2, 3-indan-2-carboxylic acid methyl ester can be efficiently and cyclically catalyzed and oxidized to prepare S-configured 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester with the optical purity of 99.7 percent.
Description
Technical Field
The invention relates to the technical field of coordination chemistry and chiral chemistry, in particular to an asymmetric chiral ligand and a preparation method thereof, a prepared catalyst, a synthesis method and application thereof.
Background
Indoxacarb (indoxacarb) is a carbamate pesticide with an oxadiazine structure, and because the molecular structure of the indoxacarb contains a chiral carbon atom, the indoxacarb has enantiomers of R and S configurations, but only indoxacarb with S-configuration has insecticidal activity. In order to efficiently prepare indoxacarb with insecticidal activity, most of the currently adopted synthetic routes are to asymmetrically catalyze and convert 5-chloro-1-oxo-2, 3-indan-2-carboxylic acid methyl ester (beta-indenone acid ester for short) into (2S) -5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester (key intermediate of indoxacarb) so as to synthesize single S-configuration indoxacarb. The catalysts used in the asymmetric catalytic conversion reaction are mainly cinchona alkaloid derivatives, chiral phosphine Schiff base-Cu (I), tartaric acid-derived chiral guanidine, chiral Salen-Zr complex, chiral Zr-Salen polymer, S-timolol derivatives and the like, but the chiral catalysts have the defects of unstable structure, few active sites, high preparation cost and the like, and severely restrict the synthesis of indoxacarb, so that research and development of heterogeneous catalysts with stable framework structure, dense active sites and excellent catalytic effect are needed to be used for synthesizing chiral key intermediates of indoxacarb.
Metal-organic framework Materials (MOFs) are organic-inorganic hybrid crystalline materials with periodic network structures formed by coordination of functionalized organic ligands and metal ions, and the structure and function of the materials can be realized by reasonably selecting and regulating the structure of the organic ligands and the types of the metal ions, so that the materials become ideal platforms for constructing catalysts with different structures and functions. Particularly, the introduction of chirality into a porous metal-organic framework is helpful for developing a solid phase chiral catalyst with asymmetric catalytic function, for example, a prolinol derivative induced chiral MOFs material with asymmetric catalytic function is disclosed in Chinese patent application publication No. CN101830920A, and can be used as a heterogeneous catalyst for asymmetric cyanation reaction, so that the catalyst can be recycled, the yield is up to 100%, and the ee value is up to 99%; the Chinese patent application publication No. CN103301885A discloses a preparation method of chiral POM/MOFs with asymmetric catalysis, which has the advantages of simple synthesis, easy operation, low raw material price, high yield, stable chemical property of the obtained functional material and easy large-area popularization and application. MOFs catalytic material has large specific surface area, the use amount only needs seven thousandth of the substrate, and the MOFs catalytic material has good conversion rate and stereoselectivity and is suitable for the requirement of industrial mass production. Nevertheless, designing and synthesizing a chiral polynuclear metal-organic framework solid phase catalyst with stable framework structure, dense active sites and excellent catalytic effect still faces great challenges at present, and the efficient chiral polynuclear metal-organic framework catalyst which can be successfully applied to asymmetric conversion of beta-indenonacid ester into (2S) -5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is more rare.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a brand-new asymmetric chiral ligand, and provide a brand-new chiral polynuclear copper metal-organic framework catalyst which has a stable structure, dense active sites and excellent catalytic effect in the process of converting beta-indenonacid ester into S-configuration 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester by high enantioselectivity.
The invention solves the technical problems by the following technical means:
an asymmetric chiral ligand having the structural formula:
the invention also provides a preparation method of the asymmetric chiral ligand, which comprises the following steps: dissolving 3-tertiary butyl-5-aldehyde-4-hydroxybenzoic acid and L-phenylalaninol in methanol, carrying out reflux reaction, and filtering while the reaction is hot after the reaction is finished to obtain the asymmetric chiral ligand.
Preferably, the chemical structural formula of the 3-tertiary butyl-5-aldehyde-4-hydroxybenzoic acid is as follows:the preparation can be carried out according to the method described in the document J.Am.chem.Soc. 2010.132 (43): 15390-15398, comprising in particular the following steps:
4-hydroxy-3-tert-butylbenzoic acid (1.55 g,7.95 mmol) was charged with hexamethylenetetramine (2.23 g,15.9 mmol) in a 250mL round bottom flask, then trifluoroacetic acid (63 mL) was added and the solution heated to reflux for 18 h. 50mL of 33% H by mass fraction is then added 2 SO 4 Added to the reaction and the solution was refluxed for an additional 3 hours. After the reaction was completed, the mixed solution was diluted with diethyl ether and washed with water, brine, and then the organic phase was dried over magnesium sulfate, and concentrated in vacuo to give 1.2 g of 3-tert-butyl-5-aldehyde-4-hydroxybenzoic acid.
Preferably, the molar ratio of the 3-tertiary butyl-5-aldehyde group-4-hydroxybenzoic acid to the L-phenylalaninol is 1:1.2 to 1.5.
Preferably, the reflux reaction is carried out for a period of time ranging from 5 to 10 hours.
The invention also provides a chiral polynuclear copper metal-organic framework catalyst prepared by adopting the asymmetric chiral ligand as a ligand, wherein the chemical formula of the chiral polynuclear copper metal-organic framework catalyst is Cu 3 L 2 Wherein L has the structural formula shown below:
the unit cell parameters of the chiral polynuclear copper metal-organic framework catalyst are as follows: the space group is P3 2 ，α＝β＝90°，γ＝120°，Z＝3。
The invention adopts an asymmetric Schiff base chiral ligand H with a tridentate chelating site 3 L (i.e., (S, E) -3- (tert-butyl) -4-hydroxy-5- ((1-hydroxy-3-phenylpropane-2-yl) imino) methyl) benzoic acid) as a bridging unit to construct a chiral metal-organic framework catalyst having a trinuclear copper structure; the ligand H 3 L is obtained by reflux reaction of 3-tertiary butyl-5-aldehyde-4-hydroxybenzoic acid and L-phenylalaninol in methanol; the chiral ligand and the metal copper ion in the chiral polynuclear copper metal-organic framework catalyst monocrystal structure are connected in the following manner;
wherein n is any integer;
the beneficial effects are that: the chiral polynuclear copper metal-organic framework catalyst has a framework formed by trinuclear Cu with 4-connection function 3 O 8 N 2 The cluster is formed by interconnecting 4 chiral asymmetric Schiff bases around the cluster. The catalyst structure has a 1.03nm hydrophobic chiral pore canal, wherein a coordination unsaturated metallic copper site is periodically inlaid, and the catalyst structure can be used as a potential recyclable solid phase chiral catalyst.
The invention also provides a synthesis method of the chiral polynuclear copper metal-organic framework catalyst, which comprises the steps of taking copper salt as metal salt, taking the asymmetric chiral ligand as an organic bridging ligand, carrying out coordination reaction by taking N, N' -dimethylformamide and methanol as solvents, cooling to room temperature after the reaction is finished, and then placing a reaction product in ice water bath for cooling to obtain the chiral polynuclear copper metal-organic framework catalyst.
The beneficial effects are that: the chiral polynuclear copper metal-organic framework catalyst prepared by the method adopts a secondary cooling crystallization method, is simple, saves time in reaction and can be prepared in a large quantity.
Preferably, the synthesis method of the chiral polynuclear copper metal-organic framework catalyst comprises the following steps:
s1, mixing copper salt, N' -dimethylformamide and methanol, then dropwise adding the mixture into a methanol solution of the asymmetric chiral ligand, heating and stirring the mixture to remove blue turbid matters, and taking a blue clarified liquid;
s2, sealing the blue clarified liquid in the S1 in a high-pressure reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, cooling to room temperature after the reaction is finished, and cooling the reaction product in an ice water bath to obtain the chiral polynuclear copper metal-organic framework catalyst.
Preferably, the molar ratio of the asymmetric chiral ligand to copper salt is 1:1.5-3; the volume ratio of N, N' -dimethylformamide, methanol for dissolving copper salt and methanol for dissolving asymmetric chiral ligand is 1:1-3:1-3; the temperature of the solvothermal reaction is 90-110 ℃ and the time is 1-2.5h.
Preferably, the molar ratio of the asymmetric chiral ligand to copper salt is 1:2; the temperature of the solvothermal reaction is 100 ℃ and the time is 1h.
Preferably, the volume ratio of N, N' -dimethylformamide, methanol dissolving copper salt, methanol dissolving asymmetric chiral ligand is 1:2:1.
preferably, the copper salt is Cu (OAc) 2 ·H 2 O、Cu(ClO 4 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O、CuCl 2 ·2H 2 A mixture of one or more of O.
Preferably, the copper salt is Cu (OAc) 2 ·H 2 O。
Preferably, in S1, the blue turbidity is removed after heating to 35-45℃and stirring for 25-35 min.
Preferably, in S1, the blue haze is removed after heating to 40℃and stirring for 30 min.
The invention also provides application of the chiral polynuclear copper metal-organic framework catalyst in preparing S-configuration 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester by asymmetrically catalyzing and oxidizing 5-chloro-1-oxo-2, 3-indane-2-carboxylic acid methyl ester.
Preferably, the oxidant used is cumene hydroperoxide; the solvent is toluene; the temperature of the reaction was room temperature.
Preferably, the ratio of the amounts of the oxidizing agent used to the substance of the reaction substrate methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate is from 1.3 to 1.7:1, a step of; the mass ratio of the chiral polynuclear copper metal-organic framework catalyst to the reaction substrate 5-chloro-1-oxo-2, 3-indan-2-carboxylic acid methyl ester is 1:25.
preferably, the ratio of the amounts of the oxidizing agent used to the substance of the reaction substrate methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate is 1.5:1.
the beneficial effects are that: the amount of the oxidant is 1.5 times that of the reaction substrate, namely, the 5-chloro-1-oxo-2, 3-indan-2-carboxylic acid methyl ester, so that the yield of the oxidant is reduced by more than 1.5 times without obvious change.
The beneficial effects are that: the chiral polynuclear copper metal-organic framework catalyst provided by the invention can be used for preparing S-configuration 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester by catalytic oxidation of 5-chloro-1-oxo-2, 3-indane-2-carboxylic acid methyl ester with 99.7% of enantioselectivity and 93% of yield, and can be recycled for multiple times without losing activity.
The chiral polynuclear copper metal-organic framework catalyst of the invention takes Cu as a metal center and chiral ligand H 3 L is a three-dimensional structure crystal with nano hydrophobic chiral pore canal formed by secondary cooling crystallization, and the molecular formula of the crystal is Cu 3 L 2 Wherein chiral ligand H 3 L is (S, E) -3- (tert-butyl) -4-hydroxy-5- ((1-hydroxy-3-phenylpropane-2-yl) imino) methyl) benzoic acid; h 3 L is of the structure
The invention has the advantages that: the chiral multi-core copper metal-organic framework catalyst is prepared by adopting a secondary cooling crystallization method, is simple and time-saving, and can be prepared in a large amount; the catalyst structure has a hydrophobic chiral pore canal with the size of 1.03nm, and is inlaid with catalytic activity metallic copper sites at high density, so that beta-indenone acid ester can be simply and efficiently catalyzed and oxidized to prepare a key intermediate S-configuration-5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester of single-configuration indoxacarb, and the catalyst can be recycled for multiple times.
Drawings
FIG. 1 shows an asymmetric chiral ligand H prepared in example 1 of the present invention 3 Nuclear magnetic spectrum of L;
FIG. 2 is a diagram showing the coordination and connection of copper ions in the chiral polynuclear copper metal-organic framework catalyst prepared in example 1 of the present invention;
FIG. 3 is a three-dimensional porous structure of the chiral multi-core copper metal-organic framework catalyst prepared in example 1 of the present invention;
FIG. 4 shows a chiral polynuclear copper metal-organic framework catalyst and chiral ligand H according to example 1 of the present invention 3 L infrared spectrogram;
FIG. 5 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the catalytic reaction product in example 4 of the present invention;
FIG. 6 is a high performance liquid chromatography of the catalytic reaction product of example 4 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
Asymmetric chiral ligand H 3 L is synthesized by the following specific steps: 3-tert-butyl-5-aldehyde-4-hydroxybenzoic acid (2.2 g,10 mmol) and L-phenylalaninol (1.8 g,12 mmol) were dissolved in 30mL of methanol, and the mixture was refluxed for 5 hours, filtered while it was still hot to obtain yellowThe color solid is the asymmetric chiral ligand H 3 L, 80% yield; for the prepared asymmetric chiral ligand H 3 The nuclear magnetism of L is tested, the nuclear magnetism spectrum is shown in figure 1, 1 H NMR(600MHz,DMSO-d 6 )δ12.43(s,1H,COOH),8.40(s,1H,NCH),7.87–7.73(m,2H,2×ArH),7.29–7.07(m,5H,5×ArH),5.03(s,1H,ArOH),3.90(d,J＝5.7Hz,1H,CH 2 OH),3.67–3.60(m,2H,CH 2 OH),3.52–3.48(m,1H,NCH),3.01–2.84(m,2H,ArCH 2 ),1.35(s,9H,C(CH 3 ) 3 )。
the synthesis method of the chiral multi-core copper metal-organic framework catalyst specifically comprises the following steps:
(1) Cu (OAc) 2 ·H 2 O (399 mg,2.0 mmol) was dissolved in a mixture of 10mL DMF and 20mL methanol (MeOH) and added dropwise to the asymmetric chiral ligand H 3 L (355 mg,1.0 mmol) in MeOH (10 mL) was heated and stirred at 40℃for 30min, then filtered to remove blue haze, and the blue clear solution was sealed in a 100mL autoclave lined with polytetrafluoroethylene.
(2) The reaction vessel was heated in a high temperature oven at 100 ℃ for 1 hour to ensure adequate reaction of the metal salt and chiral ligand.
(3) Stopping heating and cooling to room temperature, then placing the blue solution in the high-pressure reaction kettle in an ice-water bath to obtain blue grain-shaped crystals, filtering, washing and air-drying to obtain the chiral polynuclear copper metal-organic framework catalyst with the yield of 60%.
The crystal structure of the chiral polynuclear copper metal-organic framework catalyst obtained in example 1 was measured.
The measuring method comprises the following steps: the method comprises the steps of collecting data of a single crystal sample with proper size by adopting an Shanghai light source synchrotron radiation technology, reducing the obtained diffraction data by using APEX3 software, analyzing and finishing a crystal structure by using a SHELXS-2014 program, determining all non-hydrogen atoms by a full matrix least squares method (full-matrix least-squares refinement based on F2) and finishing anisotropic finishing of the atoms, wherein the hydrogen atoms on an asymmetric chiral ligand framework are finished by theoretical hydrogenation.
Measurement results: the unit cell parameters of the chiral polynuclear copper metal-organic framework catalyst single crystal of the invention are as follows: the space group is P3 2 ，α＝β＝90°，γ＝120°，Z＝3。
By analyzing the single crystal data of the chiral polynuclear copper metal-organic framework catalyst, the chiral P3 crystallized in the trigonal system can be known 2 A space group whose asymmetric unit comprises 2 metal ligand CuL units with independent crystal phases and one Cu (II) ion. As shown in FIG. 2, the two metal ligand CuL units with independent crystal phases and the Cu (II) ion form a Cu under the bridging action of the terminal carboxyl groups of the other two CuL ligands 3 O 8 N 2 Is a trinuclear copper metal cluster of (a). The Cu (II) ions in 2 metal ligands CuL in the trinuclear copper cluster take a four-coordinated twisted planar structure, while the other 1 Cu (II) ions take a four-coordinated twisted tetrahedral structure. The trinuclear copper cluster can be used as a 4-connected node to be connected with 4 surrounding ligands to form a chiral metal-organic framework with a three-dimensional structure, 1 chiral channel with the size of 1.03nm is arranged along a c-axis, hydrophobic groups such as tertiary butyl, benzene rings and the like are fully distributed in the chiral channel, and coordination unsaturated metallic copper ions are embedded in high density, as shown in figure 3, the structure is similar to a chiral pocket of metalloenzyme, so that the trinuclear copper cluster can be used as a potential asymmetric catalyst. In addition, by comparing the infrared spectrograms of the chiral ligand and the chiral polynuclear copper metal-organic framework catalyst (shown in figure 4), the chiral polynuclear copper metal-organic framework catalyst can be found to be 1675cm -1 The characteristic vibration peak of the chiral ligand carboxyl disappears, and the coordination of the metal copper ion and the ligand can be proved, which is consistent with the analysis result of the single crystal structure.
Example 2
The synthesis method of the chiral multi-core copper metal-organic framework catalyst specifically comprises the following steps:
(1) Cu (OAc) 2 ·H 2 O (1.5 mmol) was dissolved in a mixed solution of 10mL DMF and 10mL MeOH and added dropwise to the asymmetric chiral ligand H 3 L (355 mg,1.0 mmol) in MeOH (10 mL) was heated and stirred at 35℃for 25 min, then filtered to remove blue haze, and the blue clear solution was sealed in a 100mL autoclave lined with polytetrafluoroethylene.
(2) The reaction vessel was heated in a high temperature oven at 110 ℃ for 1.5 hours to ensure adequate reaction of the metal salt and chiral ligand.
(3) Stopping heating and cooling to room temperature, then placing the blue solution in the high-pressure reaction kettle in an ice-water bath to obtain blue grain-shaped crystals, filtering, washing and air-drying to obtain the chiral polynuclear copper metal-organic framework catalyst.
Example 3
The synthesis method of the chiral multi-core copper metal-organic framework catalyst specifically comprises the following steps:
(1) Cu (OAc) 2 ·H 2 O (3.0 mmol) was dissolved in a mixed solution of 10mL DMF and 30mL MeOH and added dropwise to the asymmetric chiral ligand H 3 L (355 mg,1.0 mmol) in MeOH (30 mL) was heated and stirred at 45℃for 25 min, then filtered to remove blue haze, and the blue clear solution was sealed in a 100mL autoclave lined with polytetrafluoroethylene.
(2) The reaction vessel was heated in a high temperature oven at 90 ℃ for 2 hours to ensure adequate reaction of the metal salt and chiral ligand.
(3) Stopping heating and cooling to room temperature, then placing the blue solution in the high-pressure reaction kettle in an ice-water bath to obtain blue grain-shaped crystals, filtering, washing and air-drying to obtain the chiral polynuclear copper metal-organic framework catalyst.
Example 4
The synthesis method of the chiral multi-core copper metal-organic framework catalyst specifically comprises the following steps:
(1) Cu (OAc) 2 ·H 2 O (3.0 mmol) was dissolved in a mixed solution of 10mL DMF and 15mL MeOH and added dropwise to the asymmetric chiral ligandBody H 3 L (355 mg,1.0 mmol) in MeOH (20 mL) was heated and stirred at 40℃for 35min, then filtered to remove blue haze, and the blue clear solution was sealed in a 100mL autoclave lined with polytetrafluoroethylene.
(2) The reaction vessel was heated in a high temperature oven at 105 ℃ for 2.5 hours to ensure adequate reaction of the metal salt and chiral ligand.
(3) Stopping heating and cooling to room temperature, then placing the blue solution in the high-pressure reaction kettle in an ice-water bath to obtain blue grain-shaped crystals, filtering, washing and air-drying to obtain the chiral polynuclear copper metal-organic framework catalyst.
Example 5
The synthesis method of the chiral multi-core copper metal-organic framework catalyst specifically comprises the following steps:
cu (ClO) 4 ) 2 ·6H 2 O (2.0 mmol) was dissolved in a mixed solution of 10mL DMF and 30mL MeOH and added dropwise to the asymmetric chiral ligand H 3 L (355 mg,1.0 mmol) in MeOH (30 mL) was heated at 45℃for 25 min, filtered to remove blue haze, and the blue clear solution was sealed in a 100mL autoclave lined with polytetrafluoroethylene, and the autoclave was heated in a high temperature oven at 90℃for 2 hours. Stopping heating and cooling to room temperature, then placing the blue solution in the high-pressure reaction kettle in an ice-water bath to obtain blue grain-shaped crystals, filtering, washing and air-drying to obtain the chiral polynuclear copper metal-organic framework catalyst.
Example 6
The synthesis method of the chiral multi-core copper metal-organic framework catalyst specifically comprises the following steps:
cu (NO) 3 ) 2 ·3H 2 O (2.0 mmol) was dissolved in a mixed solution of 10mL DMF and 30mL MeOH and added dropwise to the asymmetric chiral ligand H 3 L (355 mg,1.0 mmol) in MeOH (30 mL) at 45deg.C for 25 min, filtering to remove blue turbidity, sealing the blue clear solution in a 100mL autoclave lined with polytetrafluoroethylene, and heating at 90deg.C in a high temperature ovenThe reaction vessel was heated and the reaction was continued for 2 hours. Stopping heating and cooling to room temperature, then placing the blue solution in the high-pressure reaction kettle in an ice-water bath to obtain blue grain-shaped crystals, filtering, washing and air-drying to obtain the chiral polynuclear copper metal-organic framework catalyst.
Example 7
The synthesis method of the chiral multi-core copper metal-organic framework catalyst specifically comprises the following steps:
CuCl is added 2 ·2H 2 O (2.0 mmol) was dissolved in a mixed solution of 10mL DMF and 30mL MeOH and added dropwise to the asymmetric chiral ligand H 3 L (355 mg,1.0 mmol) in MeOH (30 mL) was heated at 45℃for 25 min, filtered to remove blue haze, and the blue clear solution was sealed in a 100mL autoclave lined with polytetrafluoroethylene, and the autoclave was heated in a high temperature oven at 90℃for 2 hours. Stopping heating and cooling to room temperature, then placing the blue solution in the high-pressure reaction kettle in an ice-water bath to obtain blue grain-shaped crystals, filtering, washing and air-drying to obtain the chiral polynuclear copper metal-organic framework catalyst.
Comparative example 1
When dimethyl sulfoxide (DMSO) was used instead of DMF in example 1, tetrahydrofuran was used instead of methanol in example 1, and other conditions and procedures were kept consistent with example 1, the target chiral polynuclear copper metal-organic framework catalyst crystals in the form of blue rice grains were not obtained.
Example 8
Asymmetric catalytic oxidation of methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate to S-configured methyl 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate the route is as follows:
in view of the existence of open hydrophobic chiral nanopores and rich catalytic active sites in chiral polynuclear copper metal-organic framework catalysts, we examined their ability to asymmetrically catalyze the oxidation of methyl β -indenonate 5-chloro-1-oxo-2, 3-indan-2-carboxylate. The specific experimental process is as follows: 2.24 g (10 mmol) of methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate, 25mL of toluene and 90 mg of chiral polynuclear copper metal-organic framework catalyst prepared in example 1 of the invention are stirred and mixed for 30 minutes, then 2.28 g (15 mmol) of Cumene Hydroperoxide (CHP) is added into the mixed reaction solution to react for 3 hours at room temperature, the catalyst is recovered by filtration, and after concentration of the filtrate, 2.23g of white solid is obtained by separation through a silica gel chromatographic column, namely the target product S-configuration of methyl 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate (yield 93% and nuclear magnetism is shown in FIG. 5). The high performance liquid chromatography analysis shows that the optical purity is 99.7% as shown in figure 6. After the chiral polynuclear copper metal-organic framework catalyst after filtration and recovery is washed by anhydrous acetone and naturally air-dried, the reaction can be continuously catalyzed, and the result shows that the yield after the fifth catalytic reaction is still up to 90%, and the optical purity of the product can be still maintained.
Example 9
The difference from example 8 is that: in the specific experimental process, the cumene hydroperoxide is 13mmol; when the chiral polynuclear copper metal-organic framework catalyst is 90 mg, the yield of target products is reduced to about 85%.
Example 10
The difference from example 8 is that: in the specific experimental process, the cumene hydroperoxide is 17mmol; when the chiral polynuclear copper metal-organic framework catalyst is 90 mg, the yield of the target product is kept at about 93% without obvious increase.
Comparative example 2
The difference from example 8 is: in the specific experimental process, when the oxidant is replaced by hydrogen peroxide with the same mass, other reaction conditions are kept unchanged, and the catalytic oxidation reaction hardly obtains a target product with high optical purity.
Comparative example 3
When the amounts of the substances of the oxidizing agent CHP and of the reaction substrate 5-chloro-1-oxo-2, 3-indan-2-carboxylic acid methyl ester were adjusted to 1: at 1, the catalytic reaction yield is significantly reduced. Specific embodiment As follows, 2.24 g (10 mmol) of methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate, 25mL of toluene, 90 mg of the chiral polynuclear copper metal-organic framework catalyst of example 1 of the invention are stirred and mixed for 30 minutes, then 1.52 g (10 mmol) of CHP is added dropwise to the above mixed reaction solution to react for 3 hours at room temperature, the catalyst is recovered by filtration, and after concentration of the filtrate, 1.80 g of the target product is separated by a silica gel column, the yield is about 75%.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An asymmetric chiral ligand, characterized in that: the structural formula is as follows:
2. a method of preparing an asymmetric chiral ligand according to claim 1, wherein: the method comprises the following steps: dissolving 3-tertiary butyl-5-aldehyde-4-hydroxybenzoic acid and L-phenylalaninol in methanol, carrying out reflux reaction, and filtering while the reaction is hot after the reaction is finished to obtain the asymmetric chiral ligand.
3. A chiral polynuclear copper metal-organic framework catalyst characterized by: prepared by using the asymmetric chiral ligand as defined in claim 1, which has a chemical formula of Cu 3 L 2 Wherein L has the structural formula shown below:
the unit cell parameters of the chiral polynuclear copper metal-organic framework catalyst are as follows: the space group is P3 2 ，α＝β＝90°，γ＝120°，Z＝3。
4. A method for synthesizing the chiral multi-core copper metal-organic framework catalyst according to claim 3, which is characterized in that: copper salt is used as metal salt, the asymmetric chiral ligand is used as an organic bridging ligand, N' -dimethylformamide and methanol are used as solvents for coordination reaction, after the reaction is finished, the reaction product is cooled to room temperature, and then the reaction product is placed in ice water bath for cooling, so that the chiral polynuclear copper metal-organic framework catalyst is obtained.
5. The method for synthesizing the chiral multi-core copper metal-organic framework catalyst according to claim 4, which is characterized in that: the method comprises the following steps:
s1, mixing copper salt, N' -dimethylformamide and methanol, then dropwise adding the mixture into a methanol solution of the asymmetric chiral ligand, heating and stirring the mixture to remove blue turbid matters, and taking a blue clarified liquid;
s2, sealing the blue clarified liquid in the S1 in a high-pressure reaction kettle with a polytetrafluoroethylene lining for solvothermal reaction, cooling to room temperature after the reaction is finished, and cooling the reaction product in an ice water bath to obtain the chiral polynuclear copper metal-organic framework catalyst.
6. The method for synthesizing the chiral multi-core copper metal-organic framework catalyst according to claim 5, wherein the method comprises the following steps of: the molar ratio of the asymmetric chiral ligand to the copper salt is 1:1.5-3; the volume ratio of N, N' -dimethylformamide, methanol for dissolving copper salt and methanol for dissolving asymmetric chiral ligand is 1:1-3:1-3; the temperature of the solvothermal reaction is 90-110 ℃ and the time is 1-2.5h.
7. The synthesis method of the chiral multi-core copper metal-organic framework catalyst according to any one of claims 4 to 6, wherein: the copper salt is Cu (OAc) 2 ·H 2 O、Cu(ClO 4 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O、CuCl 2 ·2H 2 A mixture of one or more of O.
8. Use of a chiral polynuclear copper metal-organic framework catalyst according to claim 3 for the asymmetric catalytic oxidation of methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate for the preparation of S-configured methyl 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-inden-2-carboxylate.
9. The use of a chiral polynuclear copper metal-organic framework catalyst according to claim 8 for the asymmetric catalytic oxidation of methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate for the preparation of S-configured methyl 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate, characterized in that: the oxidant is cumene hydroperoxide; the solvent is toluene; the temperature of the reaction was room temperature.
10. Use of a chiral polynuclear copper metal-organic framework catalyst according to claim 8 or 9 for the asymmetric catalytic oxidation of methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate for the preparation of S-configuration methyl 5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-inden-2-carboxylate, characterized in that: the ratio of the amounts of the oxidizing agent used to the substance of the reaction substrate methyl 5-chloro-1-oxo-2, 3-indan-2-carboxylate is 1.3-1.7:1, a step of; the mass ratio of the chiral polynuclear copper metal-organic framework catalyst to the reaction substrate 5-chloro-1-oxo-2, 3-indan-2-carboxylic acid methyl ester is 1:25.
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