CN114632551B - Difunctional chiral catalyst and preparation method and application thereof - Google Patents

Difunctional chiral catalyst and preparation method and application thereof Download PDF

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CN114632551B
CN114632551B CN202210162720.2A CN202210162720A CN114632551B CN 114632551 B CN114632551 B CN 114632551B CN 202210162720 A CN202210162720 A CN 202210162720A CN 114632551 B CN114632551 B CN 114632551B
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吴瑞姣
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Southeast University
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    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
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Abstract

The invention discloses a bifunctional chiral catalyst, a preparation method and application thereof, wherein the bifunctional chiral catalyst is Pd-SCNP@DUT-67-Pro, and is formed by doping Pd into single-chain nano particles (SCNP) and wrapping the Pd into pore channels of DUT-67 connected with L-proline on Zr clusters. The invention also discloses a method for preparing the bifunctional chiral catalyst. The synthesized bifunctional chiral catalyst Pd-SCNP@DUT-67-Pro has high coupling conversion rate and enantioselectivity in one-pot bell wood coupling-asymmetric aldol condensation tandem reaction. The preparation condition of the invention is mild, and the prepared product has good catalytic activity and cycle stability.

Description

Difunctional chiral catalyst and preparation method and application thereof
Technical Field
The invention relates to a bifunctional chiral catalyst, a preparation method and application thereof, and belongs to the technical field of organic chemistry.
Background
Chiral molecules refer to molecules that cannot themselves mirror with themselves. Chiral molecules also play an important role in the field of asymmetric synthesis, and their synthesis and use have been of great interest to middle-surgeon workers. The two enantiomers of chiral compounds differ significantly in physical, chemical, pharmacological and toxicity properties. Typically, one of the enantiomers of a chiral molecule has better physiological activity, in contrast to the other enantiomer, which may not be active or even have detrimental physiological activity. In order to avoid the damage to human body caused by different enantiomers of chiral molecules in medicines, the synthesis and separation of pure enantiomers have become an indispensable part in the research and development of medicines. Under this requirement, the selective synthesis of high enantiomeric excess compounds has become critical to current chiral molecular studies.
In asymmetric catalytic reaction, L-proline is widely used due to the characteristics of good catalytic effect, stable performance, mild and controllable reaction conditions and the like. However, L-proline catalysis also has the disadvantages of large amounts, non-recyclability, narrow substrate ranges, etc., which limit the high enantiomeric excess of the compounds to varying degrees. Meanwhile, the one-pot sequential reaction avoids the repeated purification process in the reaction process, has the characteristics of high efficiency, strong atomic economy, green sustainable property and the like, and is significant in meaning in chemical synthesis. The use of a Metal Organic Framework (MOF) functionalized with L-proline as a heterogeneous catalyst in asymmetric catalysis has made a major breakthrough in solving the above problems. The MOF has strong chemical stability and thermal stability and has a metal site coordinated with chiral organic ligand; meanwhile, metal nano particles and the like can be introduced into the pore structure of the catalyst, so that the catalyst can be used as an enantioselective one-pot catalytic reaction catalyst.
Disclosure of Invention
The invention aims to: to solve the above-mentioned technical problems in the background art, a first object of the present invention is to provide a bifunctional, heterogeneous chiral catalyst that can be used in a one-pot bell wood coupling-asymmetric aldol condensation tandem reaction; a second object of the present invention is to provide a process for the preparation of said bifunctional chiral catalyst. A third object of the present invention is to provide the use of said bifunctional chiral catalyst in a log coupling-asymmetric catalytic reaction.
The technical scheme is as follows: the invention provides a bifunctional chiral catalyst Pd-SCNP@DUT-67-Pro, which is obtained by loading Pd-SCNP in a MOF pore canal and then loading L-proline on a Zr cluster on the MOF.
Further, the bifunctional chiral catalyst Pd-SCNP@DUT-67-Pro is a bifunctional heterogeneous chiral catalyst which can be used for one-pot bell wood coupling-asymmetric aldol condensation tandem reaction.
The preparation method of the bifunctional chiral catalyst Pd-SCNP@DUT-67-Pro comprises the following steps:
ZrOCl 2 ·8H 2 O is dissolved in acetic acid aqueous solution to obtain ZrOCl 2 ·8H 2 O acetic acid aqueous solution, dissolving 2, 5-thiophene dicarboxylic acid in ethanol to obtain 2, 5-thiophene dicarboxylic acid ethanol solution, and adding ZrOCl 2 ·8H 2 Mixing O acetic acid aqueous solution and 2, 5-thiophene dicarboxylic acid ethanol solution, adding L-proline and Pd-SCNP, stirring, heating for reaction, washing the obtained solid with ethanol, and drying to obtain Pd-SCNP@DUT-67-Pro.
Further, the ZrOCl 2 ·8H 2 The molar ratio of O, 2, 5-thiophenedicarboxylic acid, L-proline and Pd-SCNP is 20:30:50-100:1.
Further, the volume ratio of acetic acid to water in the acetic acid aqueous solution is 1:1-1.5.
Further, the preparation method of the Pd-SCNP comprises the following steps:
(1) Heating and stirring styrene, 4- (chloromethyl) styrene, 2-azo-bis-easy-butyronitrile and 2-cyanopropyl-2-yl benzodisulfide in a nitrogen atmosphere, cooling, dissolving with tetrahydrofuran, adding dropwise into cold methanol to precipitate, repeatedly dissolving and resolving the precipitate, and drying the precipitate to obtain S1;
(2) Dissolving p-iodobenzoic acid and palladium acetate in anhydrous acetonitrile, adding triethylamine and diphenylphosphine which are subjected to distillation treatment, heating and refluxing under nitrogen atmosphere, removing a solvent to obtain a product A, dissolving the product A in KOH solution, extracting with diethyl ether to obtain a water layer, regulating the pH of the water layer with HCl solution, extracting with dichloromethane to obtain an organic layer, drying the organic layer with anhydrous magnesium sulfate, and evaporating the organic layer to obtain diphenylphosphine benzoic acid;
(3) Dissolving S1, diphenyl phosphonic benzoic acid and potassium carbonate in anhydrous N, N-dimethylformamide, heating and stirring in a nitrogen atmosphere to obtain a product B, diluting the product B with diethyl ether, extracting with saturated NaCl solution to obtain an organic phase, drying the organic phase with anhydrous sodium sulfate, removing the solvent to obtain a solid, dissolving the solid with tetrahydrofuran, dropwise adding the solid into cold methanol to precipitate, and drying the precipitate to obtain S2;
(4) S2 is dissolved in anhydrous dichloromethane to obtain S2 dichloromethane solution, the S2 dichloromethane solution is dripped into the anhydrous dichloromethane solution in which (1, 5-cyclooctadiene) palladium dichloride is dissolved under stirring, the stirring is continued to obtain mixed solution, the mixed solution is concentrated in vacuum to obtain concentrated mixed solution, the concentrated mixed solution and the concentrated mixed solution are dropwise added into cold methanol, the solid product is obtained through sedimentation, and the solid product is dried in vacuum to obtain Pd-SCNP.
Further, in the step (1), the structural general formula of S1 is shown as formula (I):
further, in the step (3), the structural general formula of S2 is as shown in formula (ii):
further, in the step (1), the molar ratio of the styrene, the 4- (chloromethyl) styrene, the 2-cyanopropyl-2-yl benzodisulfide and the 2, 2-azobisisobutyronitrile is 880:100:5:1-0.5.
Further, in the step (2), the molar ratio of the triethylamine to the paraiodobenzoic acid to the diphenylphosphine to the palladium acetate is 1000:500:500:1-0.5.
Further, in the step (3), the molar ratio of the S1 to the diphenyl phosphine benzoic acid to the potassium carbonate is 2:1:2-1.
Further, in the step (4), the molar ratio of the S2 to the (1, 5-cyclooctadiene) palladium dichloride is 2:1-0.5.
The invention also comprises the application of the bifunctional chiral catalyst in the ring wood coupling-asymmetric aldol condensation tandem reaction.
Double-function chiral catalyst bell wood coupling-asymmetric catalytic reaction mechanism: pd-SCNP loaded in the pore canal of DUT-67 is used as an active site of suzuki coupling reaction, and L-proline connected on Zr cluster is used as an active site of asymmetric aldol reaction to play a role in one-pot tandem reaction. The specific reaction mechanism simulation is shown in figure 1, in the reaction system, monosubstituted bromobenzene and 4-formylphenylboric acid are taken as reactants to enter a pore canal of DUT-67, and bell wood coupling reaction is carried out under the catalysis of Pd-SCNP to generate 4-biphenyl formaldehyde with corresponding substituent groups; and then, carrying out asymmetric aldol reaction on the 4-biphenyl formaldehyde and cyclopentanone in a reaction system under the catalysis of an L-proline active site of a catalyst to generate a corresponding asymmetric aldol product.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The invention adopts a one-pot synthesis method to load Pd-SCNP in a MOF pore canal and load L-proline on a Zr cluster, thus synthesizing the difunctional heterogeneous chiral catalyst Pd-SCNP@DUT-67-Pro which can be used for one-pot bell wood coupling-asymmetric aldol condensation tandem reaction.
(2) The synthesized bifunctional catalyst Pd-SCNP@DUT-67-Pro shows high coupling conversion rate and zirconium enantiomer selectivity in a one-pot bell wood coupling-asymmetric aldol condensation tandem reaction, and can be recycled for multiple times.
(3) The preparation method provided by the invention has mild preparation conditions, and the prepared product has good catalytic activity and cycle stability.
Drawings
FIG. 1 is a diagram of a mechanism of a dual-function chiral catalyst bell wood coupling-asymmetric catalytic reaction;
FIG. 2 is an X-ray diffraction pattern of Pd-SCNP@DUT-67-Pro powder;
FIG. 3 is Pd-SCNP@DUT-67-Pro and DUT-67. N 2 Adsorption-desorption profiles;
FIG. 4 is Pd-SCNP@DUT-67-Pro and DUT-67. N 2 Adsorption-desorption pore size distribution map;
FIG. 5 is a nuclear magnetic resonance of Pd-SCNP@DUT-67-Pro after digestion 1 H-NMR chart;
FIG. 6 is a FT-IR spectrum of Pd-SCNP@DUT-67-Pro and DUT-67;
FIG. 7 is an SEM image of Pd-SCNP@DUT-67-Pro and DUT-67;
FIG. 8 is an elemental analysis map of Pd-SCNP@DUT-67-Pro;
FIG. 9 is a graph of the catalytic performance and cycle performance test of Pd-SCNP@DUT-67-Pro.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
(1) 10.2ml of styrene, 1.4ml of 4- (chloromethyl) styrene, 110.5mg of 2-cyanopropyl-2-yl benzodisulfide and 16.4mg of 2, 2-azobisisobutyronitrile are taken and heated under nitrogen atmosphere at 90 ℃ with stirring for 24 hours; after the mixture is cooled to room temperature and dissolved by tetrahydrofuran, the mixture is added into cold methanol dropwise to precipitate out the mixture; and repeatedly dissolving and precipitating for three times, and drying to obtain S1.
(2) 1.86g of p-iodobenzoic acid and 3.4mg of palladium acetate are taken and dissolved in anhydrous acetonitrile, 2.08ml of triethylamine and 1.3ml of diphenylphosphine which are distilled are added, and after reflux for 72 hours under nitrogen atmosphere and at 95 ℃, the solvent is removed by a rotary evaporator; dissolving the product in 1mol/L KOH solution, and extracting with diethyl ether for three times; the pH of the aqueous layer obtained was adjusted to 2-3 with HCl solution and extracted three times with dichloromethane; the resulting organic layer was dried over anhydrous magnesium sulfate and evaporated by rotary evaporator to give diphenylphosphinobenzoic acid.
(3) 1.32g of S1 in the step (1), 0.46g of diphenylphosphinobenzoic acid in the step (2) and 0.42g of potassium carbonate are dissolved in anhydrous N, N-dimethylformamide, and stirred for 16 hours under the nitrogen atmosphere and 50 ℃; after diluting the resulting product with diethyl ether, it was extracted three times with saturated NaCl solution. Drying the obtained organic phase with anhydrous sodium sulfate, and removing the solvent by a rotary evaporator; the obtained solid is dissolved by tetrahydrofuran, then is added into cold methanol dropwise to precipitate and separate out, and is dried to obtain S2.
(4) 62mg of S2 in the step (3) is dissolved in anhydrous dichloromethane; another 6mg of (1, 5-cyclooctadiene) palladium dichloride was dissolved in anhydrous dichloromethane; dropwise adding the former into the latter under stirring, and continuously stirring for 1 hour; after vacuum concentration, the liquid is added into cold methanol drop by drop; the solid obtained by sedimentation is dried in vacuum to obtain Pd-SCNP.
(5) 1.23g ZrOCl was taken 2 ·8H 2 O is dissolved in acetic acid aqueous solution (the volume ratio of acetic acid to water is 1:1); 1.0g of 2, 5-thiophenedicarboxylic acid was taken and dissolved in ethanol; mixing the two solutions, adding 2.3g L-proline and 200mg of Pd-SCNP in the step (4) into the mixed solution, stirring for 10 minutes, and reacting with 80 ℃ for 48 hours; the resulting solid was washed three times with ethanol and dried to give Pd-SCNP@DUT-67-Pro.
Example 2
The resulting Pd-SCNP@DUT-67-Pro was subjected to X-ray diffraction analysis (scanning speed: 4 DEG/min, angle 5-50 DEG), and the results were shown in FIG. 2. FIG. 2 is an X-ray diffraction pattern of Pd-SCNP@DUT-67-Pro powder, wherein (a) is simulated DUT-67; (b) a synthesized DUT-67; (c) Pd-SCNP@DUT-67-Pro; (d) Pd-SCNP@DUT-67-Pro recovered after 3 times of recycling. As can be seen from FIG. 2, the diffraction peaks of the experimentally synthesized DUT-67 are strong and completely coincide with the analog standard card of the DUT-67. After Pd-SCNP and L-proline were introduced into DUT-67, the diffraction peaks of DUT-67 were not reduced, i.e., the crystal pattern was not destroyed. After three catalytic cycles, the Pd-SCNP@DUT-67-Pro still maintains a strong diffraction peak and a stable crystal structure.
Example 3
The catalyst Pd-SCNP@DUT-67-Pro obtained in example 1 was characterized by nitrogen adsorption-desorption experiments at 77K (detected by a scientific compass test platform), and the results are shown in FIGS. 3 and 4. FIG. 3 is a graph showing the adsorption-desorption of N2 from Pd-SCNP@DUT-67-Pro and DUT-67. As can be seen from FIG. 3, pd-SCNP@DUT-67-ProType I adsorption behavior similar to DUT-67 is shown, indicating that catalyst formation does not alter the micropore characteristics of the material. In addition, the BET specific surface area of Pd-SCNP@DUT-67-Pro was reduced from 1415.67m2g-1 to 589.56m2g-1 and the pore volume was reduced from 0.5932cm2g-1 to 0.2759cm2g-1, because Pd-SCNP was successfully immobilized within the MOF channel, resulting in a reduction in specific surface area and pore volume. These results also indicate that the supported material is not distributed on the surface of the porous material, but rather is distributed inside the porous material, leaving room for catalysis. FIG. 4 is a diagram of Pd-SCNP@DUT-67-Pro and N of DUT-67 2 The adsorption-desorption pore size distribution, as can be seen in FIG. 4, shows a significant decrease in pore size for Pd-SCNP@DUT-67-Pro compared to DUT-67, indicating that Pd-SCNP has been successfully immobilized within the MOF channel, resulting in a decrease in pore volume.
Example 4
By comparing the nuclear magnetism of the Pd-SCNP@DUT-67-Pro sample obtained in example 1 after digestion 1 H-NMR confirmed the presence of L-proline and Pd-SCNP in the catalyst Pd-SCNP@DUT-67-Pro. The test was performed by 600MHz nuclear magnetic resonance spectrometer. 15mg of Pd-SCNP@DUT-67-Pro sample was weighed, 5 drops of DCl (30 wt%), 15mg of CsF and 1mL of DMSO-d were added 6 Stirring is carried out for 6 hours. Then filtering out residue from the digested solution, and performing nuclear magnetism 1 H-NMR test. The results are shown in FIG. 5. FIG. 5 is a nuclear magnetic resonance of Pd-SCNP@DUT-67-Pro after digestion 1 As can be seen from the H-NMR chart in FIG. 5, peaks of L-proline appear at 4.17ppm, 3.1ppm and 1.83ppm, peaks belonging to Pd-SCNP appear at 2.17ppm and 2.24ppm, indicating successful loading of proline and Pd-SCNP in the composite catalyst Pd-SCNP@DUT-67-Pro.
Example 5
The catalyst Pd-SCNP@DUT-67-Pro synthesized in example 1 was subjected to qualitative analysis and structure exploration by using Fourier-infrared (FT-IR), potassium bromide tablets were used for testing, air was used as a background, and the obtained results are shown in FIG. 6. FIG. 6 shows FT-IR spectra of Pd-SCNP@DUT-67-Pro and DUT-67. As can be seen from FIG. 6, the infrared absorption peaks of the catalyst Pd-SCNP@DUT-67-Pro are similar to those of pure DUT-67. Wherein 1655cm -1 Characteristic band of the occurrence of the tensile vibration c=o bond, 1573cm -1 The characteristic peak of N-H bond shear deformation vibration appears, and 1257cm -1 Stretching vibration of the C-N bond was observed at 522cm -1 The presence of Zr-O bond absorption peaks is shown. By nuclear magnetism 1 H-NMR and Fourier-IR (FT-IR) tests confirmed the successful loading of L-proline with nanoparticulate Pd-SCNP in DUT-67.
Example 6
The morphology of Pd-SCNP@DUT-67-Pro obtained in example 1 was analyzed using a Scanning Electron Microscope (SEM) (detected by a scientific compass test platform). As a result, FIG. 7 shows an SEM image of Pd-SCNP@DUT-67-Pro and DUT-67, where (a) is DUT-67; (b) Pd-SCNP@DUT-67-Pro. As can be seen from FIG. 7, the morphology of DUT-67 and Pd-SCNP@DUT-67-Pro is spherical, with a size of about 2.5 microns (a-b). It was further verified that the morphology of DUT-67 was unchanged after the single-stranded nanoparticles Pd-SCNP and L-proline were introduced.
Example 7
EDS elemental analysis (detected by a scientific compass test platform) was performed on Pd-SCNP@DUT-67-Pro obtained in example 1, and the results are shown in FIG. 8, wherein FIG. 8 is an elemental analysis chart of Pd-SCNP@DUT-67-Pro, and the EDS elemental analysis shows the elemental distribution of Zr, pd, S, N, O, P, respectively. Wherein, P is a special element in Pd-SCNP, and DUT-67 and L-proline do not contain P element, so the P element appears in EDS element analysis of composite catalyst Pd-SCNP@DUT-67-Pro, and the successful loading of single-chain nano particles Pd-SCNP can be further verified. The even distribution of N element in the EDS element analysis is that the L-proline is successfully coordinated with the MOF zirconium cluster, and another important evidence that the bifunctional catalyst Pd-SCNP@DUT-67-Pro is successfully synthesized
Example 8
(1) 10.2ml of styrene, 1.4ml of 4- (chloromethyl) styrene, 110.5mg of 2-cyanopropyl-2-yl benzodisulfide and 12.3mg of 2, 2-azobisisobutyronitrile are taken and heated under nitrogen atmosphere at 90 ℃ with stirring for 24 hours; after the mixture is cooled to room temperature and dissolved by tetrahydrofuran, the mixture is added into cold methanol dropwise to precipitate out the mixture; and repeatedly dissolving and precipitating for three times, and drying to obtain S1.
(2) 1.86g of p-iodobenzoic acid and 2.6mg of palladium acetate are taken and dissolved in anhydrous acetonitrile, 2.08ml of triethylamine and 1.3ml of diphenylphosphine which are distilled are added, and after reflux for 72 hours under nitrogen atmosphere and at 95 ℃, the solvent is removed by a rotary evaporator; dissolving the product in 1mol/L KOH solution, and extracting with diethyl ether for three times; the pH of the aqueous layer obtained was adjusted to 2-3 with HCl solution and extracted three times with dichloromethane; the resulting organic layer was dried over anhydrous magnesium sulfate and evaporated by rotary evaporator to give diphenylphosphinobenzoic acid.
(3) 1.32g of S1 in the step (1), 0.46g of diphenylphosphinobenzoic acid in the step (2) and 0.32g of potassium carbonate are dissolved in anhydrous N, N-dimethylformamide, and stirred for 16 hours under the nitrogen atmosphere and 50 ℃; after diluting the resulting product with diethyl ether, it was extracted three times with saturated NaCl solution. Drying the obtained organic phase with anhydrous sodium sulfate, and removing the solvent by a rotary evaporator; the obtained solid is dissolved by tetrahydrofuran, then is added into cold methanol dropwise to precipitate and separate out, and is dried to obtain S2.
(4) 62mg of S2 in the step (3) is dissolved in anhydrous dichloromethane; another 4.5mg of (1, 5-cyclooctadiene) palladium dichloride was dissolved in anhydrous dichloromethane; dropwise adding the former into the latter under stirring, and continuously stirring for 1 hour; after vacuum concentration, the liquid is added into cold methanol drop by drop; the solid obtained by sedimentation is dried in vacuum to obtain Pd-SCNP.
(5) 1.23g ZrOCl was taken 2 ·8H 2 O is dissolved in acetic acid aqueous solution (the volume ratio of acetic acid to water is 1:1.25); 1.0g of 2, 5-thiophenedicarboxylic acid was taken and dissolved in ethanol; mixing the two solutions, adding 1.7-g L-proline and 200mg of Pd-SCNP in the step (4) into the mixed solution, stirring for 10 minutes, and reacting with 80 ℃ for 48 hours; the resulting solid was washed three times with ethanol and dried to give Pd-SCNP@DUT-67-Pro.
Example 9
(1) 10.2ml of styrene, 1.4ml of 4- (chloromethyl) styrene, 110.5mg of 2-cyanopropyl-2-yl benzodisulfide and 8.2mg of 2, 2-azobisisobutyronitrile are taken and heated under nitrogen atmosphere at 90 ℃ with stirring for 24 hours; after the mixture is cooled to room temperature and dissolved by tetrahydrofuran, the mixture is added into cold methanol dropwise to precipitate out the mixture; and repeatedly dissolving and precipitating for three times, and drying to obtain S1.
(2) 1.86g of p-iodobenzoic acid and 1.7mg of palladium acetate are taken and dissolved in anhydrous acetonitrile, 2.08ml of triethylamine and 1.3ml of diphenylphosphine which are distilled are added, and after reflux for 72 hours under nitrogen atmosphere and at 95 ℃, the solvent is removed by a rotary evaporator; dissolving the product in 1mol/L KOH solution, and extracting with diethyl ether for three times; the pH of the aqueous layer obtained was adjusted to 2-3 with HCl solution and extracted three times with dichloromethane; the resulting organic layer was dried over anhydrous magnesium sulfate and evaporated by rotary evaporator to give diphenylphosphinobenzoic acid.
(3) 1.32g of S1 in the step (1), 0.46g of diphenylphosphinobenzoic acid in the step (2) and 0.21g of potassium carbonate are dissolved in anhydrous N, N-dimethylformamide, and stirred for 16 hours under the nitrogen atmosphere and 50 ℃; after diluting the resulting product with diethyl ether, it was extracted three times with saturated NaCl solution. Drying the obtained organic phase with anhydrous sodium sulfate, and removing the solvent by a rotary evaporator; the obtained solid is dissolved by tetrahydrofuran, then is added into cold methanol dropwise to precipitate and separate out, and is dried to obtain S2.
(4) 62mg of S2 in the step (3) is dissolved in anhydrous dichloromethane; another 3mg of (1, 5-cyclooctadiene) palladium dichloride was dissolved in anhydrous dichloromethane; dropwise adding the former into the latter under stirring, and continuously stirring for 1 hour; after vacuum concentration, the liquid is added into cold methanol drop by drop; the solid obtained by sedimentation is dried in vacuum to obtain Pd-SCNP.
(5) 1.23g ZrOCl was taken 2 ·8H 2 O is dissolved in acetic acid aqueous solution (the volume ratio of acetic acid to water is 1:1.5); 1.0g of 2, 5-thiophenedicarboxylic acid was taken and dissolved in ethanol; mixing the two solutions, adding 1.2-g L-proline and 200mg of Pd-SCNP in the step (4) into the mixed solution, stirring for 10 minutes, and reacting with 80 ℃ for 48 hours; the resulting solid was washed three times with ethanol and dried to give Pd-SCNP@DUT-67-Pro.
Example 10 catalytic Performance and cycle Performance test of bifunctional chiral catalyst Pd-SCNP@DUT-67-Pro
The catalyst Pd-SCNP@DUT-67-Pro prepared in the embodiment 1 of the invention is applied to the bell wood coupling-asymmetric aldol reaction, and specifically comprises the following steps:
(1) 1mmol bromobenzene, 1.2mmol 4-formylphenylboronic acid and 0.2mmol K are weighed out 2 CO 3 0.4mL of the mixture was added at a volume ratio of 11, adding a catalyst Pd-SCNP@DUT-67-Pro 20mg into a mixed solution of toluene and water;
(2) The mixture is kept at 80 ℃ for 3 hours;
(3) After the heat preservation is finished, a small amount of concentrated hydrochloric acid is dripped to adjust the reaction system to a neutral environment, 1.6mL of toluene and 0.88mL of cyclopentanone are added, and after 10 minutes of ultrasound, the reaction system is subjected to heat preservation for 7 days at 10 ℃;
(4) After the heat preservation is finished, the filtrate is purified by a column, wherein the filling agent is silica gel, the mobile phase is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 4:1, and the ee value and dr value of the product are measured by chiral high performance liquid chromatography (the chromatographic column is AD-H, the mobile phase is chromatographic pure hexane: isopropanol=90:10, and the flow rate is 0.8 mL/min).
As shown in FIG. 9, FIG. 9 shows the catalytic performance and cycle performance test chart of Pd-SCNP@DUT-67-Pro, and as can be seen from FIG. 9, the bifunctional catalyst Pd-SCNP@DUT-67-Pro still maintains good catalytic performance after three cycles of use, and the coupling yields of one-pot tandem reaction are 75%, 72% and 63%, respectively, and the ee of the asymmetric product is obtained anti The values are respectively: 77%, 68% and 61%. In addition, as can be seen from the PXRD graph, the framework structure of the catalyst MOFs is not changed after three times of recycling.
In addition, bromobenzene can be replaced by monosubstituted bromobenzene in the embodiment, and the substituent is 4-CH 3 、4-CH 3 O、4-CN、4-NO 2 . The results are shown in Table 1.
TABLE 1 catalytic Performance for one pot tandem reactions
As can be seen from Table 1, the Pd-SCNP@DUT-67-Pro was used to catalyze the one-pot tandem bell wood coupling-asymmetric aldol reaction, and when the reactant was 4-formylphenylboronic acid and bromobenzene with substituents listed in the table, both the bell wood coupling yield and the asymmetric reaction yield were higher, and at the same time, the asymmetric product had a high ee value. The excellent catalytic performance of Pd-SCNP@DUT-67-Pro in one-pot series bell wood coupling-asymmetric aldol reaction is demonstrated.

Claims (9)

1. The method is characterized in that the Pd-SCNP@DUT-67-Pro of the bifunctional chiral catalyst is obtained by loading Pd-SCNP in a MOF pore canal and then loading L-proline on a Zr cluster on the MOF, and the Pd-SCNP preparation comprises the following steps:
(1) Heating and stirring styrene, 4- (chloromethyl) styrene, 2-azo-bis-easy-butyronitrile and 2-cyanopropyl-2-yl benzodisulfide in a nitrogen atmosphere, cooling, dissolving with tetrahydrofuran, adding dropwise into cold methanol to precipitate, repeatedly dissolving and resolving the precipitate, and drying the precipitate to obtain S1;
(2) Dissolving p-iodobenzoic acid and palladium acetate in anhydrous acetonitrile, adding triethylamine and diphenylphosphine which are subjected to distillation treatment, heating and refluxing under nitrogen atmosphere, removing a solvent to obtain a product A, dissolving the product A in KOH solution, extracting with diethyl ether to obtain a water layer, regulating the pH of the water layer with HCl solution, extracting with dichloromethane to obtain an organic layer, drying the organic layer with anhydrous magnesium sulfate, and evaporating the organic layer to obtain diphenylphosphine benzoic acid;
(3) Dissolving S1, diphenyl phosphonic benzoic acid and potassium carbonate in anhydrous N, N-dimethylformamide, heating and stirring in a nitrogen atmosphere to obtain a product B, diluting the product B with diethyl ether, extracting with saturated NaCl solution to obtain an organic phase, drying the organic phase with anhydrous sodium sulfate, removing the solvent to obtain a solid, dissolving the solid with tetrahydrofuran, dropwise adding the solid into cold methanol to precipitate, and drying the precipitate to obtain S2;
(4) S2 is dissolved in anhydrous dichloromethane to obtain S2 dichloromethane solution, the S2 dichloromethane solution is dripped into the anhydrous dichloromethane solution in which (1, 5-cyclooctadiene) palladium dichloride is dissolved under stirring, the stirring is continued to obtain mixed solution, the mixed solution is concentrated in vacuum to obtain concentrated mixed solution, the concentrated mixed solution and the concentrated mixed solution are dropwise added into cold methanol, the solid product is obtained through sedimentation, and the solid product is dried in vacuum to obtain Pd-SCNP.
2. Preparation of the bifunctional chiral catalyst of claim 1The method is characterized by comprising the following steps: zrOCl 2 ·8H 2 O is dissolved in acetic acid aqueous solution to obtain ZrOCl 2 ·8H 2 O acetic acid aqueous solution, dissolving 2, 5-thiophene dicarboxylic acid in ethanol to obtain 2, 5-thiophene dicarboxylic acid ethanol solution, and adding ZrOCl 2 ·8H 2 Mixing O acetic acid aqueous solution and 2, 5-thiophene dicarboxylic acid ethanol solution, adding L-proline and Pd-SCNP, stirring, heating for reaction, washing the obtained solid with ethanol, and drying to obtain Pd-SCNP@DUT-67-Pro.
3. The method according to claim 2, wherein the ZrOCl is 2 ·8H 2 The mol ratio of O, 2, 5-thiophene dicarboxylic acid, L-proline and Pd-SCNP is 20:30:50-100:1; the volume ratio of acetic acid to water in the acetic acid aqueous solution is 1:1-1.5.
4. The preparation method according to claim 2, wherein the preparation of Pd-SCNP comprises the steps of:
(1) Heating and stirring styrene, 4- (chloromethyl) styrene, 2-azo-bis-easy-butyronitrile and 2-cyanopropyl-2-yl benzodisulfide in a nitrogen atmosphere, cooling, dissolving with tetrahydrofuran, adding dropwise into cold methanol to precipitate, repeatedly dissolving and resolving the precipitate, and drying the precipitate to obtain S1;
(2) Dissolving p-iodobenzoic acid and palladium acetate in anhydrous acetonitrile, adding triethylamine and diphenylphosphine which are subjected to distillation treatment, heating and refluxing under nitrogen atmosphere, removing a solvent to obtain a product A, dissolving the product A in KOH solution, extracting with diethyl ether to obtain a water layer, regulating the pH of the water layer with HCl solution, extracting with dichloromethane to obtain an organic layer, drying the organic layer with anhydrous magnesium sulfate, and evaporating the organic layer to obtain diphenylphosphine benzoic acid;
(3) Dissolving S1, diphenyl phosphonic benzoic acid and potassium carbonate in anhydrous N, N-dimethylformamide, heating and stirring in a nitrogen atmosphere to obtain a product B, diluting the product B with diethyl ether, extracting with saturated NaCl solution to obtain an organic phase, drying the organic phase with anhydrous sodium sulfate, removing the solvent to obtain a solid, dissolving the solid with tetrahydrofuran, dropwise adding the solid into cold methanol to precipitate, and drying the precipitate to obtain S2;
(4) S2 is dissolved in anhydrous dichloromethane to obtain S2 dichloromethane solution, the S2 dichloromethane solution is dripped into the anhydrous dichloromethane solution in which (1, 5-cyclooctadiene) palladium dichloride is dissolved under stirring, the stirring is continued to obtain mixed solution, the mixed solution is concentrated in vacuum to obtain concentrated mixed solution, the concentrated mixed solution and the concentrated mixed solution are dropwise added into cold methanol, the solid product is obtained through sedimentation, and the solid product is dried in vacuum to obtain Pd-SCNP.
5. The method of claim 4, wherein in step (1), the general structural formula of S1 is as shown in formula (I):
6. the method according to claim 4, wherein in the step (3), the structural general formula of S2 is represented by formula (II):
7. the process according to claim 4, wherein in the step (1), the molar ratio of styrene, 4- (chloromethyl) styrene, 2-cyanopropyl-2-ylbenzodisulfide and 2, 2-azobisisobutyronitrile is 880:100:5:1-0.5; in the step (2), the molar ratio of the triethylamine to the paraiodobenzoic acid to the diphenylphosphine to the palladium acetate is 1000:500:500:1-0.5.
8. The method according to claim 4, wherein in the step (3), the molar ratio of S1, diphenylphosphinobenzoic acid and potassium carbonate is 2:1:2-1; in the step (4), the molar ratio of the S2 to the (1, 5-cyclooctadiene) palladium dichloride is 2:1-0.5.
9. Use of the bifunctional chiral catalyst of claim 1 in a log coupling-asymmetric aldol condensation tandem reaction.
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