CN109046465B - Preparation and application of mesoporous silicon material immobilized chiral gold catalyst - Google Patents
Preparation and application of mesoporous silicon material immobilized chiral gold catalyst Download PDFInfo
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- CN109046465B CN109046465B CN201810826393.XA CN201810826393A CN109046465B CN 109046465 B CN109046465 B CN 109046465B CN 201810826393 A CN201810826393 A CN 201810826393A CN 109046465 B CN109046465 B CN 109046465B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
The invention discloses a preparation method and application of a mesoporous silicon material immobilized chiral gold catalyst, which are characterized in that an alkenyl functional group chiral imine phosphine ligand and sulfydryl functional SBA-15 or MCM-41 are immobilized and react for 8-12 h at the temperature of 80-110 ℃ to obtain a functional mesoporous silicon material, and the functional mesoporous silicon material reacts with dimethyl sulfide aurous chloride and THF at room temperature to obtain the mesoporous silicon material immobilized chiral gold catalyst, wherein the catalyst has good catalytic activity and enantioselectivity in asymmetric cycloaddition reaction of eneyne and nitrone. Compared with the prior art, the method has the advantages of simple synthesis steps, easy separation of the catalyst, good cyclicity, high-order two-dimensional hexagonal mesoporous structure of the formed catalyst with the coordination of the functionalized mesoporous silicon material and the gold, large specific surface area, uniform pore size distribution and the like, and has huge development potential and application prospect in the field of heterogeneous catalysis.
Description
Technical Field
The invention relates to the technical field of mesoporous silicon material immobilized chiral gold catalysts, in particular to a preparation method of a recyclable heterogeneous mesoporous silicon material immobilized chiral gold catalyst and application of the recyclable heterogeneous mesoporous silicon material immobilized chiral gold catalyst in asymmetric cycloaddition reaction of eneynone and nitrone.
Background
In recent years, a gold compound of a chiral phosphine ligand is rapidly developed and is most widely applied to asymmetric catalysis, but the application of the gold compound of the chiral phosphine ligand is limited due to the high price of gold and the chiral ligand, and the design and synthesis of a recyclable chiral phosphine ligand gold catalyst is a hotspot of current research. An effective way to solve this problem is to prepare a heterogeneous catalyst of a chiral phosphine ligand gold compound.
At present, the research on the gold compound of the chiral phosphine ligand is in homogeneous catalysis, and the research on heterogeneous catalysis is less. The Zjunliang problem group (ACS Catal.2015,5, 7488-.
The gold heterogeneous catalyst of the chiral phosphine ligand in the prior art is easy to oxidize and difficult to separate, and the activity cannot be maintained after the catalyst is recycled.
Disclosure of Invention
The invention aims to provide a preparation method and application of a mesoporous silicon material immobilized chiral gold catalyst aiming at the defects of the prior art, wherein a mercapto-introduced mesoporous silicon material is reacted with an olefin functionalized chiral imine phosphine ligand, the obtained functionalized mesoporous silicon material is reacted with dimethyl sulfide aurous chloride to generate the mesoporous silicon material immobilized chiral gold catalyst, and the catalyst has good catalytic activity and enantioselectivity in the asymmetric cycloaddition reaction of eneyne and nitrone, is simple to prepare, is easy to separate and can be recycled.
The specific technical scheme for realizing the purpose of the invention is as follows: a preparation method of a mesoporous silicon material immobilized chiral gold catalyst is characterized in that an alkenyl functionalized chiral imine phosphine ligand and azo diisobutyronitrile (AIBN), toluene and mercapto functionalized mesoporous silicon material are reacted for 8-12 hours at the temperature of 80-110 ℃, after the reaction is finished, filtrate is sequentially washed by toluene and diethyl ether, then vacuum drying is carried out for 8-12 hours at the temperature of 80-110 ℃, the chiral imine phosphine ligand functionalized mesoporous silicon material is obtained, and the chiral imine phosphine ligand functionalized mesoporous silicon material, dimethyl sulfide aurous chloride and Tetrahydrofuran (THF) are subjected to a molar volume ratio of 1 mmol: 1.2 mmol-1.5 mmol: 5-10 mL of the mixture is mixed and reacted for 2-4 hours at room temperature to carry out the reaction with the following reaction structural formula:
in the formula: r1Is an alkyl olefin or phenyl olefin; r2Is an alkyl olefin or phenyl olefin;
after the reaction is finished, washing the filtrate with THF and ether in sequence, and drying for 6-8 hours in vacuum at the temperature of 60-80 ℃ to obtain a product which is a mesoporous silicon material immobilized chiral gold catalyst, wherein the molar volume ratio of the chiral imine phosphine ligand to AIBN, toluene and the mesoporous silicon material is 1 mmol: 0.6-0.8 mmol: 50-60 mL: 1.5-1.8 mmol; the alkenyl group is styryl, allyl or binaphthyl; the mesoporous silicon material is SBA-15 or MCM-41.
The application of the mesoporous silicon material-immobilized chiral gold catalyst is to apply the mesoporous silicon material-immobilized chiral gold catalyst to the asymmetric cycloaddition reaction of the alkenone and the nitrone, and the reaction structural formula is as follows:
wherein: r1Is alkyl or aryl, R2Is alkyl or aryl; r3Is aryl; r4Is alkyl or aryl; r5Is alkyl or aryl;
the asymmetric cycloaddition reaction of the eneynone and the nitrone is to make mesoporous silicon material carry chiral gold catalyst and AgNTf2Dissolving in dichloromethane, reacting at-10-30 ℃ for 10-20 min, adding eneynone and nitrone, reacting at-10-30 ℃ for 3-8 h, filtering out the catalyst after the reaction is finished, washing the filtrate for several times by acetone, combining organic phases, drying, filtering, concentrating and carrying out column chromatography to obtain the product of furan compounds, washing and drying the filtered catalyst for reuse, wherein the eneynone, nitrone and mesoporous silicon materialsMaterial-supported chiral gold catalyst and AgNTf2And dichloromethane in a molar volume ratio of 1 mmol: 1.2-1.3 mmol: 0.3-0.5 mmol: 0.3-0.5 mmol: 1-2 mL.
Compared with the prior art, the method has the advantages of simple synthesis steps, easy separation of the catalyst, good cyclicity, high catalytic activity in the asymmetric cycloaddition reaction of the eneynone and the nitrone, easy separation, recycling and the like, and the formed catalyst of the coordination of the functionalized mesoporous silicon material and the gold has a highly ordered two-dimensional hexagonal mesoporous structure, a larger specific surface area and uniform pore size distribution, is an environment-friendly heterogeneous catalyst, and has huge development potential and application prospect in the field of heterogeneous catalysis.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product prepared in example 1;
FIG. 2 shows product N prepared in example 12Adsorption-desorption isotherm plot.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Preparation of styryl functionalized chiral phosphine ligand
Weighing 1g (5.0mmol) of sulfinamidophosphine ligand and 20mL of dichloromethane in a flask, placing the flask in a low-temperature constant-temperature reaction bath at-48 ℃, slowly dripping 10mmol of styrene into the round-bottom flask, transferring the device to the room temperature condition to react for 9h after finishing dripping, and then using NH4And (3) quenching the reaction by using a Cl solution, then adding 3X 10mL of ethyl acetate for dilution, drying by using anhydrous sodium sulfate after extraction, and separating by column chromatography after spin drying to obtain 0.8g of a product which is the styryl functionalized chiral phosphine ligand.
(II) preparation of functionalized mesoporous silicon material
Under argon atmosphere, 216mg of the prepared chiral phosphorus ligand, 1.0g of mercapto-functionalized SBA-15 and 54mg of AIBN are weighed in a flask, 100mL of toluene is added after vacuum pumping, reflux is carried out for 8h at the temperature of 100 ℃, reaction liquid is washed by toluene and ether alternately after suction filtration, and 0.9g of functionalized mesoporous silicon material is obtained after vacuum drying.
Preparation of mesoporous silicon material supported chiral gold catalyst
Weighing 0.6g of the prepared mesoporous silicon material and 52mg of dimethyl sulfide chloroaniline in a flask under the argon atmosphere, pumping and exchanging gas for three times, adding 50mL of anhydrous THF solution, stirring at room temperature for 8h, after the reaction solution is pumped and filtered, washing the filtrate for three times by THF, and drying in vacuum to obtain 0.56g of a product which is a functionalized catalyst for coordination of the mesoporous silicon material and gold, namely the mesoporous silicon material immobilized chiral gold catalyst.
Referring to fig. 1, wherein: the curve a is SBA-15; curve b is mercapto-functionalized SBA-15; the curve c is a mesoporous silicon material functionalized by chiral imine phosphine ligand; the d curve is a chiral gold catalyst immobilized on a mesoporous silicon material, the product prepared in the above example 1 is characterized by an ordered two-dimensional hexagonal structure through X-ray diffraction, and the structure of the product is not damaged in the material modification process.
Referring to fig. 2, wherein: the curve a is SBA-15; curve b is mercapto-functionalized SBA-15; the curve c is a mesoporous silicon material functionalized by chiral imine phosphine ligand; the d curve is chiral gold catalyst supported by mesoporous silicon material, the specific surface areas are 668m2/g, 543m2/g,471m2/g and 398m2/g respectively, the pore volumes are 0.85cm3/g, 0.69cm3/g, 0.62cm3/g and 0.59cm3/g respectively, the product prepared in the above example 1 is characterized by nitrogen adsorption-desorption isotherm, and the specific surface area and the pore volume of the material are gradually reduced in the modification process.
Example 2
Preparation of (I) allyl functionalized chiral phosphine ligand
Weighing 5.0mmol of sulfinylamine phosphine ligand and 20mL of dichloromethane in a flask, placing the flask in a low-temperature constant-temperature reaction bath at the temperature of-48 ℃, slowly dropping 10mmol of allyl magnesium bromide into the flask, transferring the device to the room temperature condition after dropping is finished, reacting for 8 hours, and reacting with NH4And (3) quenching the reaction by using a Cl solution, then adding 3X 10mL of ethyl acetate for dilution, drying by using anhydrous sodium sulfate after extraction, and separating by column chromatography after spin drying to obtain 0.9g of a product which is the chiral phosphine ligand functionalized by allyl.
(II) preparation of functionalized mesoporous silicon material
Weighing 230mg of the prepared chiral phosphine ligand, 1.0g of sulfydryl functionalized SBA-15 and 56mg of AIBN in a flask under the argon atmosphere, vacuumizing, adding 100mL of methylbenzene, refluxing at the temperature of 95 ℃ for 7 hours, performing suction filtration on reaction liquid, alternately washing with methylbenzene and diethyl ether, and performing vacuum drying to obtain 0.89g of functionalized mesoporous silicon material.
(III) preparation of mesoporous silicon material immobilized chiral gold catalyst
Weighing 0.6g of the prepared mesoporous silicon material and 60mg of dimethyl sulfide chloroaniline in a flask under the argon atmosphere, pumping and exchanging gas for three times, adding 50mL of anhydrous THF solution, stirring for 9h at room temperature, after the reaction solution is pumped and filtered, washing the filtrate for three times by THF, and drying in vacuum to obtain 0.53g of a product which is a functionalized catalyst for coordination of the mesoporous silicon material and gold, namely the mesoporous silicon material immobilized chiral gold catalyst.
Example 3
Preparation of (I) binaphthyl vinyl functionalized chiral phosphine ligand
Putting 5.0mmol of sulfinylamine phosphine ligand and 20mL of dichloromethane into a flask, putting the flask into a low-temperature constant-temperature reaction bath at the temperature of-48 ℃, slowly dropping 10mmol of dinaphthalene ethylene magnesium bromide into the flask, transferring the device to the room temperature condition to react for 10 hours after the dropping is finished, and then using NH4And (3) quenching the reaction by using a Cl solution, then adding 3X 10mL of ethyl acetate for dilution, drying by using anhydrous sodium sulfate after extraction, and separating by column chromatography after spin drying to obtain 0.6g of a product which is the binaphthyl vinyl functionalized chiral phosphine ligand.
(II) preparation of functionalized mesoporous silicon material
And under the argon atmosphere, weighing 200mg of the prepared chiral phosphine ligand, 1.0g of sulfydryl functionalized SBA-15 and 53mg of AIBN into a flask, vacuumizing, adding 100mL of methylbenzene, refluxing for 6h at the temperature of 105 ℃, performing suction filtration on reaction liquid, alternately washing with methylbenzene and diethyl ether, and performing vacuum drying to obtain 0.85g of functionalized mesoporous silicon material.
(III) preparation of mesoporous silicon material immobilized chiral gold catalyst
Under the argon atmosphere and the argon atmosphere, 0.6g of the prepared mesoporous silicon material and 55mg of dimethyl sulfide chloroaniline are weighed and placed in a flask, after the gas is pumped and exchanged for three times, 50mL of anhydrous THF solution is added, the mixture is stirred for 9 hours at room temperature, after the reaction liquid is pumped and filtered, the filtrate is washed with THF for three times and then dried in vacuum, and 0.49g of product which is the functionalized catalyst for coordination of the mesoporous silicon material and the gold, namely the mesoporous silicon material immobilized chiral gold catalyst, is obtained.
Example 4
Weighing 5.5 mol% of the prepared mesoporous silicon material immobilized chiral gold catalyst and 5 mol% of AgNTf under argon atmosphere2Mixing with 1mL of DCE solution to form a reaction system, stirring for 15min at the temperature of minus 10 ℃, then mixing 0.4mmol of dissolved eneynone with 1.1eq of nitrone and 3mLDCE solution, cooling to minus 20 ℃, adding into the reaction system, reacting for 5 hours at the temperature of minus 20 ℃, filtering out the catalyst after the reaction is finished, washing the filtrate for three times by acetone, combining organic phases, carrying out vacuum spin-drying, drying and suction-filtering to obtain a crude product of the furan compound, then carrying out concentration and column chromatography to obtain 0.6mg of the furan compound, wherein the yield is 90%, the ee value is 91%, and the filtered catalyst can be reused after washing and drying.
The above embodiments are only for further illustration of the present invention and are not intended to limit the present invention, and all equivalent implementations of the present invention should be included in the scope of the claims of the present invention.
Claims (2)
1. A preparation method of a mesoporous silicon material immobilized chiral gold catalyst is characterized in that an alkenyl functionalized chiral imine phosphine ligand and azo diisobutyronitrile, toluene and mercapto functionalized mesoporous silicon material react at the temperature of 80-110 ℃ for 8-12 h, after the reaction is finished, filtrate is washed by toluene and ether in sequence, then at the temperature of 80-110 ℃, vacuum drying is carried out for 8-12 h to obtain the chiral imine phosphine ligand functionalized mesoporous silicon material, the chiral imine phosphine ligand functionalized mesoporous silicon material is mixed with dimethyl sulfide aurous chloride and tetrahydrofuran according to the molar volume ratio of 1 mmol: 1.2-1.5 mmol: 5-10 mL, and the reaction is carried out at room temperature for 2-4 h, wherein the reaction formula is as follows:
in the formula: r1Is styryl, allyl or binaphthyl; r2Is styryl, allyl or binaphthyl;
after the reaction is finished, washing the filtrate with THF and ether in sequence, and drying for 6-8 hours in vacuum at the temperature of 60-80 ℃ to obtain a product which is a mesoporous silicon material immobilized chiral gold catalyst, wherein the molar volume ratio of the chiral imine phosphorus ligand to azodiisobutyronitrile, toluene and the mesoporous silicon material is 1 mmol: 0.6-0.8 mmol: 50-60 mL: 1.5-1.8 mmol; the mesoporous silicon material is SBA-15 or MCM-41.
2. The application of the mesoporous silicon material supported chiral gold catalyst of claim 1, which is characterized in that the mesoporous silicon material supported chiral gold catalyst is applied to an asymmetric cycloaddition reaction of alkenone and nitrone, and the reaction formula is as follows:
wherein: r1Is alkyl or aryl, R2Is alkyl or aryl; r3Is aryl; r4Is alkyl or aryl; r5Is alkyl or aryl;
the asymmetric cycloaddition reaction of the eneynone and the nitrone is to make mesoporous silicon material carry chiral gold catalyst and AgNTf2Dissolving the mixture in dichloromethane, reacting at the temperature of-10 to-30 ℃ for 10-20 min, adding eneynone and nitrone, reacting at the temperature of-10 to-30 ℃ for 3-8 h, filtering out the catalyst after the reaction is finished, washing the filtrate for several times by using acetone, combining organic phases, drying, filtering, concentrating and carrying out column chromatography to obtain a furan compound serving as a product, washing and drying the filtered catalyst for reuse, wherein the eneynone, the nitrone, the mesoporous silicon material immobilized chiral gold catalyst, the AgNTf2The molar volume ratio of the dichloromethane to the dichloromethane is 1 mmol: 1.2-1.3 mmol: 0.3-0.5 mmol: 1-2 mL.
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