CN111116677A - Preparation method and application of metal-organic framework structure compound with chiral pore structure - Google Patents

Preparation method and application of metal-organic framework structure compound with chiral pore structure Download PDF

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CN111116677A
CN111116677A CN202010050378.8A CN202010050378A CN111116677A CN 111116677 A CN111116677 A CN 111116677A CN 202010050378 A CN202010050378 A CN 202010050378A CN 111116677 A CN111116677 A CN 111116677A
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段春迎
肖兵
何成
李学召
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Dalian University of Technology
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    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract

The invention belongs to the technical field of fine chemical engineering, and relates to a preparation method and application of a metal-organic framework structure compound with a chiral pore structure, wherein the preparation method is a metal-based ligand Ir (III) complex L with right-handed helical chirality1Or metal-based ligands Ir (III) complexes L chiral in a left-handed helix2Cu in tetrahedrally coordinated configuration in transition metal salts as basic building blocks+As a metal node, reacting to prepare a metal-organic framework structure compound with a chiral pore structure. The metal-organic framework structure compound with the chiral pore channel structure prepared by the method has low raw material price and high yield,is easy to be put into practical application. As compound Cu-L1Or Cu-L2The application of the N-phenyltetrahydroisoquinoline and phenylacetylene in catalyzing asymmetric oxidative dehydrogenation coupling (CDC) reaction has the yield up to 80% and the enantioselectivity greater than 50%.

Description

Preparation method and application of metal-organic framework structure compound with chiral pore structure
The invention relates to a preparation method and application of a metal-organic framework structure compound with a chiral pore structure, and belongs to the technical field of fine chemical engineering.
Background
The chiral drugs in the common chemical drugs in the world at present account for more than 60 percent, and the phenomena of strict chiral matching and molecular recognition between different isomers of chiral drug molecules and living body macromolecules can cause remarkable differences in pharmacological activity, metabolic process, toxicity and the like. In clinical treatment, the administration of the chiral drug with enantiomer purity can not only eliminate the toxic and side effects caused by invalid/bad enantiomer, but also reduce the dosage and the metabolic burden of human body to the invalid enantiomer, better control the pharmacokinetics and dosage and improve the specificity of the drug. Therefore, chiral chemical pharmacy has become a leading field of medicinal chemistry research. The chiral catalyst has structural design and function expansion, and plays a crucial role in asymmetric catalysis. Aiming at the clinical medication requirements of serious diseases such as tumor, cardiovascular and cerebrovascular diseases and the like, the key technical researches such as chiral synthesis, enzyme catalysis, crystallization control, high-end preparations, imitation drug consistency evaluation and the like are carried out, and the treatment drug with targeting property, high selectivity and new action mechanism is developed. Therefore, the development of a green and efficient asymmetric catalytic system for the precise synthesis of pharmaceutical intermediates related to the treatment of tumors and cardiovascular diseases has important social and economic significance.
Chiral tetrahydroisoquinoline chemical small molecules, particularly C1 substituted optically active structures have rich biological activity, for example, alkyl substituted tetrahydroisoquinoline analogue (+) -dysoxyline is an effective cardiotonic, and (+) -Crispine A has in vitro cytotoxic activity and antitumor activity. The synthesis process of the drug is complex in steps and low in yield, for example, the reported method for asymmetrically synthesizing (+) -dysoxyline needs 14 steps of reaction, the comprehensive yield is only about 9%, the used transition metal catalyst and chiral cocatalyst are high in cost and cannot be recycled after use, and the problems of heavy metal residue in a chiral intermediate product, environmental pollution in the production process and the like cannot be ignored. Therefore, the development of a novel simple, convenient, green and efficient asymmetric synthesis method for preparing the C1 chiral tetrahydroisoquinoline derivative has important theoretical significance and application prospect for developing a new drug lead compound.
However, reports of asymmetric cross-dehydrogenation coupling reaction catalyzed by metal are relatively few, and the methods have defects of low selectivity, harsh reaction conditions, complex operation and the like, 2004, li kork et al of McGill university report an asymmetric ethynylation reaction of copper-catalyzed tetrahydroisoquinoline for the first time, and realize introduction of a chiral group at the C1 position, under different reaction conditions, copper (I) can realize higher stereoselectivity than copper (II), on the other hand, with energy crisis influence caused by daily exhaustion of fossil fuel, chemists begin to develop a novel clean and pollution-free sunlight-driven reaction, expand photocatalysis to a reaction for synthesizing (C1 chiral) tetrahydroisoquinoline organic micromolecules, and in 2013, the beauty pearl group utilizes a complex with redox capability as a photocatalyst, realizes a chiral ligand of a chiral isoquinoline type organic micromolecule, and a chiral ligand of heterogeneous catalyst, and has great significance for the synthesis of noble metal-chiral ligand through the synergistic reaction of recycling of chiral ligand, and the chiral ligand of the chiral isoquinoline and the chiral ligand of the noble metal under the conditions of heterogeneous catalyst, and the chiral ligand of the chiral isoquinoline type organic micromolecules, and the noble metal are greatly reduced in the synthesis process of catalyzing the chiral ligand of the Pt-p ligand.
The metal-Organic Framework Structures (MOFs) are porous complexes with pores, which are constructed by organic ligands with certain rigidity and metal ions. As a novel chiral porous crystalline material, the chiral metal-organic framework structure shows diversified topological structures and excellent structural performance, and has wide application prospects in the field of heterogeneous asymmetric catalysis. On one hand, the special structure and the catalytic function of the chiral porous structure enable the chiral porous structure to have the advantages of high enzyme catalytic efficiency, high selectivity and convenient separation of heterogeneous catalytic materials such as molecular sieves, and meanwhile, the domain-limiting effect of the chiral porous structure provides possibility for completing configuration selectivity and stereoselectivity which are difficult to realize under conventional conditions. In the related work reported by Kim professor of Korean scientist in journal of Science in 2000, in a metal-organic framework structure with stable structure, a chiral organic ligand and a zinc atom form a cavity structure with one-dimensional pore channels, and the enantioselectivity of the catalytic process is improved by utilizing the limit domain effect of uncoordinated pyridine nitrogen atoms and chiral space. The Hupp professor of northwest university of America utilizes chiral Mn-salen catalytic center to construct chiral MOFs, and is applied to catalyzing olefin epoxidation, and the yield of oxidation reaction reaches 71%, and the stereoselectivity reaches 82%. Professor lingonbin, university of chicago, usa, introduced chiral binaphthol catalytic centers into MOF systems in various studies to perform various stereoselective catalytic reactions. The systems provide the assembly rule of chiral MOFs, and greatly enrich the research content and catalytic reaction of MOFs asymmetric catalysis.
According to the requirements of target catalytic reaction, the invention designs and synthesizes a chiral metal-organic framework (hp-MOFs) structure with photocatalysis and metal asymmetric catalysis centers, and is applied to the preparation of C1 chiral tetrahydroisoquinoline organic molecules under the condition of visible light. Mainly introduces single chiral cationic Ir (III) complex with excellent photo-physical-chemical properties as a basic building module, utilizes a rigid configuration chiral skeleton thereof, modifies N, P and other coordination sites at the tail end of a ring metal ligand thereof, and transmits the chiral information thereof to Cu (copper) with four coordination+Metal node, regulating and controlling metal node coordination environment, controllable construction containing optical activity and stereo selectionMOFs catalytic platform of selective confinement channels. The C-C coupling reaction of C1 chiral tetrahydroisoquinoline molecules under the conditions of photocatalysis and metal catalysis is realized by utilizing chiral channels, photocatalytic units and metal nodes with catalytic activity in a chiral environment in hp-MOFs.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method and application of a metal-organic framework structure compound with a chiral pore channel structure. The metal-organic framework structure compound prepared by the method has excellent photophysical chemical properties, keeps certain configuration chirality and coordination chirality in an internal pore channel, is beneficial to catalytic reaction and has higher enantioselectivity, so that the compound can couple a photocatalytic process and a transition metal asymmetric catalytic process in a chiral environment, and realizes asymmetric oxidative dehydrogenation coupling (CDC) reaction of tetrahydroisoquinoline molecules and aryne compounds under the double catalytic condition.
In order to achieve the above purpose and solve the problems in the prior art, the invention adopts the following technical scheme: a process for preparing the metal-organic frame compound with chiral porous structure from the right-handed spiral chiral metal-base ligand Ir (III) complex L1Or metal-based ligands Ir (III) complexes L chiral in a left-handed helix2Cu in tetrahedrally coordinated configuration in transition metal salts as basic building blocks+As a metal node, reacting to prepare a metal-organic framework structure compound with a chiral pore structure, wherein the synthetic route is as follows:
Cu++L1→Cu-L1or Cu++L2→Cu-L2
The transition metal salt is selected from one of copper tetraacetonitrile perchlorate, copper tetranitrile tetrafluoroborate, copper tetranitrile hexafluorophosphate or copper tetranitrile trifluoromethanesulfonate;
the metal-based ligand Ir (III) complex L with right-handed helical chirality1Has the following molecular structural formula (A),
Figure BDA0002370936380000041
in the formula: r1Is hydrogen, R2One selected from hydrogen, methyl, trifluoromethyl or tert-butyl, R3Is hydrogen;
the left-handed helical chiral metal-based ligand Ir (III) complex L2Has the following molecular structural formula (B),
Figure BDA0002370936380000042
Figure BDA0002370936380000051
in the formula: r1Is hydrogen, R2One selected from hydrogen, methyl, trifluoromethyl or tert-butyl, R3Is hydrogen;
the compound Cu-L1The preparation method specifically comprises the following steps:
step 1, adding 4-bromobenzoic acid, potassium carbonate and palladium acetate into 30-60 mL of mixed solvent of ethanol and water in a volume ratio of 3:1 according to a molar ratio of 1: 2-3: 0.01-0.02, adding 0.5-1.0 mL of 2-bromopyridine, reacting for 1-3 h at 75-85 ℃, cooling to room temperature, extracting with ethyl acetate and saturated saline solution, drying with anhydrous sodium sulfate, filtering, performing rotary evaporation, and passing through a silica gel column by using a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 100:1 to obtain white powder;
step 2, adding iridium trichloride and the white powder prepared in the step 1 into 30-40 mL of a mixed solvent of ethylene glycol monomethyl ether and water in a volume ratio of 3:1 according to a molar ratio of 1: 2-4, refluxing and stirring for 20-24 h at 120-130 ℃, after the reaction is finished, performing suction filtration, washing the filter cake obtained by suction filtration with a small amount of water, ethanol and diethyl ether, and performing vacuum drying on the washed filter cake to obtain yellow powder;
step 3, adding the yellow powder prepared in the step 2, sodium methoxide and L-proline into 200-600 mL of mixed solution of dichloromethane and methanol in a volume ratio of 4:1 according to a molar ratio of 1: 2-4, introducing argon, refluxing and stirring for 10-12 hours at 50 ℃, extracting with dichloromethane and saturated saline water after reaction is finished, drying, filtering and rotary evaporating, and passing through a silica gel column by using dichloromethane and ethanol solution in a volume ratio of 9:1 to obtain light yellow powder;
step 4, adding the light yellow powder prepared in the step 3 and 2, 2-bipyridine into 150-300 mL of dichloromethane solution according to a molar ratio of 1: 3-3.5, introducing argon, adding 60-150 uL of trifluoroacetic acid, stirring for 4-5 hours at 20-30 ℃, adding 2.0-3.0 g of potassium hexafluorophosphate, reacting for 4-5 hours at 20-30 ℃, extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, and performing rotary evaporation, and passing a mixed solution of dichloromethane and methanol with a volume ratio of 300:1 through a silica gel column to obtain orange yellow powder;
step 5, adding the orange powder prepared in the step 4 and 4-pyridinepinacol borate according to a molar ratio of 1: 4-5 into 30-40 mL of a mixed solvent of tetrahydrofuran and a potassium carbonate aqueous solution with a volume ratio of 2:1, introducing argon, adding 50-100 mg of tetratriphenyl phosphorodiamidate, reacting for 20-24 hours at 80-90 ℃, extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, and performing rotary evaporation, and passing the mixed solution of dichloromethane and methanol with a volume ratio of 100:1 through a silica gel column to obtain the orange powder, namely the metal-based ligand Ir (III) complex L with right-handed spiral chirality1；
Step 6, the metal-based ligand Ir (III) complex L with the right-handed helical chirality prepared in the step 51Adding the transition metal Cu salt and the transition metal Cu salt into 10-15 mL of acetonitrile solvent according to a molar ratio of 1: 2-3, stirring for 4-6 h at room temperature, filtering, standing the filtrate at room temperature for 2 weeks, and precipitating a green solid in the solution to obtain the target compound Cu-L1；
The compound Cu-L2The preparation method specifically comprises the following steps:
step 1, adding 4-bromobenzoic acid, potassium carbonate and palladium acetate into a mixed solvent of ethanol and water with a volume ratio of 3:1 of 30-70 mL according to a molar ratio of 1: 2-4: 0.01-0.03, adding 0.5-1.0 mL of 2-bromopyridine, reacting for 2-4 hours at 80-90 ℃, cooling to room temperature, extracting with ethyl acetate and saturated saline solution, drying with anhydrous sodium sulfate, filtering, performing rotary evaporation, and passing through a silica gel column by using a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 100:1 to obtain white powder;
step 2, adding iridium trichloride and the white powder prepared in the step 1 into 35-45 mL of a mixed solvent of ethylene glycol monomethyl ether and water in a volume ratio of 3:1 according to a molar ratio of 1: 2-4, refluxing and stirring for 22-24 h at 110-130 ℃, after the reaction is finished, performing suction filtration, washing the filter cake obtained by the suction filtration with a small amount of water, ethanol and diethyl ether, and performing vacuum drying on the washed filter cake to obtain yellow powder;
step 3, adding the yellow powder prepared in the step 2, sodium methoxide and D-proline into 700-1000 mL of mixed solution of dichloromethane and methanol in a volume ratio of 4:1 according to a molar ratio of 1: 2-4, introducing argon, refluxing and stirring at 50 ℃ for 11-14 hours, extracting with dichloromethane and saturated saline water after reaction is finished, drying, filtering and performing rotary evaporation, and passing through a silica gel column by using dichloromethane and ethanol solution in a volume ratio of 9:1 to obtain light yellow powder;
step 4, adding the light yellow powder prepared in the step 3 and 2, 2-bipyridine into 170-230 mL of dichloromethane solution according to a molar ratio of 1: 2-4, introducing argon, adding 100-150 uL of trifluoroacetic acid, stirring for 5-6 h at 20-30 ℃, adding 2.5-3.5 g of potassium hexafluorophosphate, reacting for 5-6 h at 30-40 ℃, extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, and performing rotary evaporation, and passing through a silica gel column by using a dichloromethane and methanol mixed solution with a volume ratio of 300:1 to obtain orange yellow powder;
step 5, adding the orange powder prepared in the step 4 and 4-pyridinepinacol borate according to a molar ratio of 1: 3-5 into 35-45 mL of a mixed solvent of tetrahydrofuran and a potassium carbonate aqueous solution with a volume ratio of 2:1, introducing argon, adding 60-120 mg of tetratriphenyl phosphorodiamidate, reacting at 85-95 ℃ for 22-24 h, extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, and performing rotary evaporation, and passing the mixed solution of dichloromethane and methanol with a volume ratio of 100:1 through a silica gel column to obtain the orange powder, namely the metal-based ligand Ir (III) complex L with left-handed spiral chirality2；
Step 6, preparing the left-handed helical chiral metal-based ligand Ir (III) complex L prepared in the step 52Adding the transition metal Cu salt and the transition metal Cu salt into 12-17 mL of acetonitrile solvent according to a molar ratio of 1: 2-4, stirring for 3-6 h at room temperature, filtering, standing the filtrate at room temperature for 3 weeks, and precipitating a green solid in the solution to obtain the target compound Cu-L2。
The compound Cu-L prepared by the preparation method1Or Cu-L2The application in catalyzing asymmetric oxidative dehydrogenation coupling (CDC) reaction of N-phenyltetrahydroisoquinoline and phenylacetylene molecules.
The invention has the beneficial effects that: a preparation method of a metal-organic framework structure compound with a chiral pore structure and an application thereof, wherein the preparation method is a metal-based ligand Ir (III) complex L with right-handed helical chirality1Or metal-based ligands Ir (III) complexes L chiral in a left-handed helix2Cu in tetrahedrally coordinated configuration in transition metal salts as basic building blocks+As a metal node, reacting to prepare a metal-organic framework structure compound with a chiral pore structure, wherein the synthetic route is as follows: cu++L1→Cu-L1Or Cu++L2→Cu-L2(ii) a The transition metal salt is selected from one of copper tetraacetonitrile perchlorate, copper tetranitrile tetrafluoroborate, copper tetranitrile hexafluorophosphate or copper tetranitrile trifluoromethanesulfonate; compared with the prior art, the metal-organic framework compound with the chiral pore structure prepared by the method has the advantages of low raw material price and high yield, and the obtained metal-organic framework compound has a chiral cavity and excellent photocatalytic property and is easy to put into practical application. As compound Cu-L1Or Cu-L2The application of the N-phenyltetrahydroisoquinoline and phenylacetylene in catalyzing asymmetric oxidative dehydrogenation coupling (CDC) reaction has the yield up to 80% and the enantioselectivity greater than 50%.
Drawings
FIG. 1 shows Cu-L as a compound of example 11Crystal structure of (2).
FIG. 2 shows Cu-L as a compound of example 11Ultraviolet-visible absorption ofA spectrogram.
FIG. 3 is the example 1 Compound Cu-L1Fluorescence emission spectrum of (a).
FIG. 4 is the metal-based ligand Ir (III) complex L of the right-handed helical chirality of example 11Is/are as follows1H NMR nuclear magnetic spectrum.
FIG. 5 is Cu-L of the Compound of example 11And example 5 Compound Cu-L2Circular dichroism spectrum of (1).
FIG. 6 shows Cu-L as a compound of example 102Catalyzing N-phenyltetrahydroisoquinoline and 4-fluorophenylacetylene to carry out asymmetric oxidative dehydrogenation coupling (CDC) reaction under illumination condition1H NMR nuclear magnetic spectrum.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
4-bromobenzeneboronic acid (2.4g,12mmol), potassium carbonate (3.32g,24mmol) and palladium acetate (36mg,0.16mmol) were added to 40mL of a 3:1 volume ratio mixed solvent of ethanol and water, followed by addition of 2-bromopyridine (790uL,8mmol), and reaction was carried out at 80 ℃ for 2 h. Cooled to room temperature, extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, filtered and rotary evaporated, and passed through a silica gel column using a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 100:1 to give 1.6g of a white powder in 86% yield. Adding iridium trichloride (762.7mg,2.54mmol) and white powder (1.5g,6.44mmol) into 30mL of mixed solvent of ethylene glycol monomethyl ether and water with the volume ratio of 3:1, refluxing and stirring at 120 ℃ for 24h, performing suction filtration after reaction, washing the filter cake obtained by suction filtration with a small amount of water, ethanol and diethyl ether, and drying the washed filter cake in vacuum to obtain 1.2g of yellow powder with the yield of 70%; adding yellow powder (900mg,0.66mmol), sodium methoxide (105.0mg,1.95mmol) and L-proline (224.1mg,1.95mmol) into 600mL of a mixed solution of dichloromethane and methanol in a volume ratio of 4:1, introducing argon, refluxing and stirring at 50 ℃ for 12h, extracting with dichloromethane and saturated saline after the reaction is finished, drying, filtering and evaporating by rotary evaporation, and passing through a silica gel column by using a mixed solution of dichloromethane and ethanol in a volume ratio of 9:1 to obtain 465mg of light yellow powder with the yield of 94%. The pale yellow powder (450mg,0.585mmol) was mixed with2, 2-bipyridine (278.7mg,1.76mmol) was added to a 225mL dichloromethane solution, after introducing argon gas, trifluoroacetic acid (130.1uL,1.76mmol) was added thereto, and the mixture was stirred at 30 ℃ for 4 hours, followed by addition of 3.0g potassium hexafluorophosphate and reaction at 30 ℃ for 4 hours. After the reaction is finished, dichloromethane and saturated saline are used for extraction, drying, filtering and rotary evaporation are carried out, and mixed solution of dichloromethane and methanol with the volume ratio of 300:1 is used for passing through a silica gel column, so that 525mg of orange yellow powder is obtained, and the yield is 94%. The orange powder (480mg,0.5mmol) and 4-pyridopinacol borate (411mg,2mmol) were added to 30mL of a mixed solvent of tetrahydrofuran and an aqueous solution of potassium carbonate at a volume ratio of 2:1, and after introducing argon gas, 100mg of tetrakistriphenylphosphine palladium was added and reacted at 80 ℃ for 24 hours. After the reaction is finished, dichloromethane and saturated saline are used for extraction, drying, filtering and rotary evaporation are carried out, a mixed solution of dichloromethane and methanol with the volume ratio of 100:1 is used for passing through a silica gel column, orange yellow powder 211mg is obtained, the yield is 44 percent, namely, the metal-based ligand Ir (III) complex L with the right-handed spiral chirality1. The metal-based ligand Ir (III) complex L with right-handed helical chirality1(24mg,0.025mmol) and copper tetraethyl cyanide perchlorate (16mg,0.05mmol) are added into 10mL acetonitrile solvent, stirred for 4h at room temperature, filtered, and the filtrate is stood at room temperature for 2 weeks to precipitate green solid in the solution, thus obtaining the target compound Cu-L123mg, yield 46%. The crystal structure is shown in figure 1.
Example 2
The metal-based ligand Ir (III) complex L with right-handed helical chirality1(24mg,0.025mmol) and copper tetrafluoroborate (15.7mg,0.05mmol) were added to 10mL of acetonitrile solvent, stirred at room temperature for 4h, filtered, and the filtrate was allowed to stand at room temperature for 2 weeks to precipitate a green solid in the solution, to obtain the desired compound Cu-L120mg, yield 40%.
Example 3
The metal-based ligand Ir (III) complex L with right-handed helical chirality1(24mg,0.025mmol) and copper (18.6mg,0.05mmol) tetraacetonitrile hexafluorophosphate were added to 10mL of acetonitrile solvent, stirred at room temperature for 4 hours, filtered, and the filtrate was allowed to stand at room temperature for 2 weeks to precipitate a green solid in the solution, to obtain the target compound Cu-L119mg, yield 38%。
Example 4
The metal-based ligand Ir (III) complex L with right-handed helical chirality1(24mg,0.025mmol) and copper (18.8mg,0.05mmol) tetraacetonitrile trifluoromethanesulfonate were added to 10mL of acetonitrile solvent, stirred at room temperature for 4h, filtered, and the filtrate was allowed to stand at room temperature for 2 weeks to precipitate a green solid in the solution, to obtain the target compound Cu-L116mg, yield 32%.
Example 5
4-bromobenzeneboronic acid (2.4g,12mmol), potassium carbonate (3.32g,24mmol) and palladium acetate (36mg,0.16mmol) are added to 70mL of a mixed solvent of ethanol and water in a volume ratio of 3:1, and then 2-bromopyridine (790uL,8mmol) is added, and the mixture is reacted at 85 ℃ for 3 hours. Cooled to room temperature, extracted with ethyl acetate and saturated brine, dried over anhydrous sodium sulfate, filtered and rotary evaporated, and passed through a silica gel column using a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 100:1 to give 1.52g of a white powder in 81% yield. Adding iridium trichloride (762.7mg,2.54mmol) and white powder (1.5g,6.44mmol) into 35mL of mixed solvent of ethylene glycol monomethyl ether and water with the volume ratio of 3:1, refluxing and stirring at 115 ℃ for 23h, performing suction filtration after reaction, washing the filter cake obtained by suction filtration with a small amount of water, ethanol and diethyl ether, and drying the washed filter cake in vacuum to obtain 1.3g of yellow powder with the yield of 76%; adding yellow powder (1.2g,0.88mmol), sodium methoxide (140.0mg,2.6mmol) and D-proline (298.8mg,2.6mmol) into 960mL of a mixed solution of dichloromethane and methanol with a volume ratio of 4:1, introducing argon, refluxing and stirring at 50 ℃ for 14h, extracting with dichloromethane and saturated saline after the reaction is finished, drying, filtering, evaporating by rotation, and passing through a silica gel column by using a mixed solution of dichloromethane and ethanol with a volume ratio of 9:1 to obtain light yellow powder 480mg with a yield of 73%. The pale yellow powder (450mg,0.59mmol) and 2, 2-bipyridine (278.7mg,1.76mmol) were added to 230mL of a dichloromethane solution, and after introducing argon gas, trifluoroacetic acid (130.1uL,1.76mmol) was added thereto, followed by stirring at 30 ℃ for 6 hours, and then 3.5g of potassium hexafluorophosphate was added thereto, followed by reaction at 35 ℃ for 5 hours. Extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, rotary evaporating, and passing through silica gel column with a mixed solution of dichloromethane and methanol at a volume ratio of 300:1 to obtain497mg orange yellow powder, 89% yield. The orange powder (480mg,0.5mmol) and 4-pyridopinacol borate (411mg,2mmol) were added to 35mL of a mixed solvent of tetrahydrofuran and an aqueous solution of potassium carbonate at a volume ratio of 2:1, and 90mg of tetrakistriphenylphosphine-palladium was added thereto after introducing argon gas and reacted at 85 ℃ for 23 hours. After the reaction is finished, dichloromethane and saturated saline are used for extraction, drying, filtering and rotary evaporation are carried out, a mixed solution of dichloromethane and methanol with the volume ratio of 100:1 is used for passing through a silica gel column, and orange yellow powder 234mg with the yield of 49 percent, namely the metal-based ligand Ir (III) complex L with the left-handed helical chirality is obtained2. The left-handed helical chiral metal-based ligand Ir (III) complex L2(24mg,0.025mmol) and copper tetraethyl cyanide perchlorate (16mg,0.05mmol) are added into 15mL acetonitrile solvent, stirred for 5h at room temperature, filtered, and the filtrate is stood at room temperature for 3 weeks to precipitate green solid in the solution, thus obtaining the target compound Cu-L227mg, yield 54%.
Example 6
The left-handed helical chiral metal-based ligand Ir (III) complex L2(24mg,0.025mmol) and copper tetrafluoroborate (15.7mg,0.05mmol) were added to 15mL of acetonitrile solvent, stirred at room temperature for 5h, filtered, and the filtrate was allowed to stand at room temperature for 3 weeks to precipitate a green solid in the solution, to obtain the target compound Cu-L220mg, yield 40%.
Example 7
The left-handed helical chiral metal-based ligand Ir (III) complex L2(24mg,0.025mmol) and copper (18.6mg,0.05mmol) tetraacetonitrile hexafluorophosphate were added to 15mL of acetonitrile solvent, stirred at room temperature for 5 hours, filtered, and the filtrate was allowed to stand at room temperature for 3 weeks to precipitate a green solid in the solution, to obtain the target compound Cu-L219mg, yield 38%.
Example 8
The left-handed helical chiral metal-based ligand Ir (III) complex L2(24mg,0.025mmol) and copper (18.8mg,0.05mmol) tetraacetonitrile trifluoromethanesulfonate were added to 15mL of acetonitrile solvent, stirred at room temperature for 5h, filtered, and the filtrate was allowed to stand at room temperature for 3 weeks to precipitate a green solid in the solution, to obtain the objective compound Cu-L216mg, yield 32%.
Example 9
Using the compound Cu-L1Catalyzing the N-phenyltetrahydroisoquinoline and phenylacetylene to carry out asymmetric oxidative dehydrogenation coupling (CDC) reaction. To the photocatalytic tube, N-phenyltetrahydroisoquinoline (20.9mg,0.1mmol), phenylacetylene (25.5mg, 0.25mmol), 2mL of dry tetrahydrofuran and the compound Cu-L were sequentially added1(2.0mg,1mmol), and reacted at room temperature for 24h under an incandescent lamp. 80% of N-phenyltetrahydroisoquinoline and phenylacetylene have asymmetric oxidative dehydrogenation coupling (CDC) reaction, and the enantioselectivity is more than 40%.
Example 10
Using the compound Cu-L2Catalyzing N-phenyltetrahydroisoquinoline and 4-fluoro phenylacetylene to carry out asymmetric oxidative dehydrogenation coupling (CDC) reaction. To the photocatalytic tube, N-phenyltetrahydroisoquinoline (20.9mg,0.1mmol), 4-fluoroacetylene (33.0mg, 0.25mmol), 2mL of dry tetrahydrofuran and the compound Cu-L were sequentially added2(2.0mg,1mmol), and reacted at room temperature for 24h under an incandescent lamp. 70% of N-phenyl-tetrahydroisoquinoline and 4-fluoro phenylacetylene have asymmetric oxidative dehydrogenation coupling (CDC) reaction, and the enantioselectivity is more than 50%.

Claims (2)

1. A preparation method of a metal-organic framework structure compound with a chiral pore structure is characterized by comprising the following steps: metal-based ligand Ir (III) complex L chiral by right-handed helix1Or metal-based ligands Ir (III) complexes L chiral in a left-handed helix2Cu in tetrahedrally coordinated configuration in transition metal salts as basic building blocks+As a metal node, reacting to prepare a metal-organic framework structure compound with a chiral pore structure, wherein the synthetic route is as follows:
Cu++L1→Cu-L1or Cu++L2→Cu-L2
The transition metal salt is selected from one of copper tetraacetonitrile perchlorate, copper tetranitrile tetrafluoroborate, copper tetranitrile hexafluorophosphate or copper tetranitrile trifluoromethanesulfonate;
the metal-based ligand Ir (III) complex L with right-handed helical chirality1Has the following structure(A) The molecular structural formula of the compound is shown in the specification,
Figure FDA0002370936370000011
in the formula: r1Is hydrogen, R2One selected from hydrogen, methyl, trifluoromethyl or tert-butyl, R3Is hydrogen;
the left-handed helical chiral metal-based ligand Ir (III) complex L2Has the following molecular structural formula (B),
Figure FDA0002370936370000012
in the formula: r1Is hydrogen, R2One selected from hydrogen, methyl, trifluoromethyl or tert-butyl, R3Is hydrogen;
the compound Cu-L1The preparation method specifically comprises the following steps:
step 1, adding 4-bromobenzoic acid, potassium carbonate and palladium acetate into 30-60 mL of mixed solvent of ethanol and water in a volume ratio of 3:1 according to a molar ratio of 1: 2-3: 0.01-0.02, adding 0.5-1.0 mL of 2-bromopyridine, reacting for 1-3 h at 75-85 ℃, cooling to room temperature, extracting with ethyl acetate and saturated saline solution, drying with anhydrous sodium sulfate, filtering, performing rotary evaporation, and passing through a silica gel column by using a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 100:1 to obtain white powder;
step 2, adding iridium trichloride and the white powder prepared in the step 1 into 30-40 mL of a mixed solvent of ethylene glycol monomethyl ether and water in a volume ratio of 3:1 according to a molar ratio of 1: 2-4, refluxing and stirring for 20-24 h at 120-130 ℃, after the reaction is finished, performing suction filtration, washing the filter cake obtained by suction filtration with a small amount of water, ethanol and diethyl ether, and performing vacuum drying on the washed filter cake to obtain yellow powder;
step 3, adding the yellow powder prepared in the step 2, sodium methoxide and L-proline into 200-600 mL of mixed solution of dichloromethane and methanol in a volume ratio of 4:1 according to a molar ratio of 1: 2-4, introducing argon, refluxing and stirring for 10-12 hours at 50 ℃, extracting with dichloromethane and saturated saline water after reaction is finished, drying, filtering and rotary evaporating, and passing through a silica gel column by using dichloromethane and ethanol solution in a volume ratio of 9:1 to obtain light yellow powder;
step 4, adding the light yellow powder prepared in the step 3 and 2, 2-bipyridine into 150-300 mL of dichloromethane solution according to a molar ratio of 1: 3-3.5, introducing argon, adding 60-150 uL of trifluoroacetic acid, stirring for 4-5 hours at 20-30 ℃, adding 2.0-3.0 g of potassium hexafluorophosphate, reacting for 4-5 hours at 20-30 ℃, extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, and performing rotary evaporation, and passing a mixed solution of dichloromethane and methanol with a volume ratio of 300:1 through a silica gel column to obtain orange yellow powder;
step 5, adding the orange powder prepared in the step 4 and 4-pyridinepinacol borate according to a molar ratio of 1: 4-5 into 30-40 mL of a mixed solvent of tetrahydrofuran and a potassium carbonate aqueous solution with a volume ratio of 2:1, introducing argon, adding 50-100 mg of tetratriphenyl phosphorodiamidate, reacting for 20-24 hours at 80-90 ℃, extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, and performing rotary evaporation, and passing the mixed solution of dichloromethane and methanol with a volume ratio of 100:1 through a silica gel column to obtain the orange powder, namely the metal-based ligand Ir (III) complex L with right-handed spiral chirality1；
Step 6, the metal-based ligand Ir (III) complex L with the right-handed helical chirality prepared in the step 51Adding the transition metal Cu salt and the transition metal Cu salt into 10-15 mL of acetonitrile solvent according to a molar ratio of 1: 2-3, stirring for 4-6 h at room temperature, filtering, standing the filtrate at room temperature for 2 weeks, and precipitating a green solid in the solution to obtain the target compound Cu-L1；
The compound Cu-L2The preparation method specifically comprises the following steps:
step 1, adding 4-bromobenzoic acid, potassium carbonate and palladium acetate into a mixed solvent of ethanol and water with a volume ratio of 3:1 of 30-70 mL according to a molar ratio of 1: 2-4: 0.01-0.03, adding 0.5-1.0 mL of 2-bromopyridine, reacting for 2-4 hours at 80-90 ℃, cooling to room temperature, extracting with ethyl acetate and saturated saline solution, drying with anhydrous sodium sulfate, filtering, performing rotary evaporation, and passing through a silica gel column by using a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 100:1 to obtain white powder;
step 2, adding iridium trichloride and the white powder prepared in the step 1 into 35-45 mL of a mixed solvent of ethylene glycol monomethyl ether and water in a volume ratio of 3:1 according to a molar ratio of 1: 2-4, refluxing and stirring for 22-24 h at 110-130 ℃, after the reaction is finished, performing suction filtration, washing the filter cake obtained by the suction filtration with a small amount of water, ethanol and diethyl ether, and performing vacuum drying on the washed filter cake to obtain yellow powder;
step 3, adding the yellow powder prepared in the step 2, sodium methoxide and D-proline into 700-1000 mL of mixed solution of dichloromethane and methanol in a volume ratio of 4:1 according to a molar ratio of 1: 2-4, introducing argon, refluxing and stirring at 50 ℃ for 11-14 hours, extracting with dichloromethane and saturated saline water after reaction is finished, drying, filtering and performing rotary evaporation, and passing through a silica gel column by using dichloromethane and ethanol solution in a volume ratio of 9:1 to obtain light yellow powder;
step 4, adding the light yellow powder prepared in the step 3 and 2, 2-bipyridine into 170-230 mL of dichloromethane solution according to a molar ratio of 1: 2-4, introducing argon, adding 100-150 uL of trifluoroacetic acid, stirring for 5-6 h at 20-30 ℃, adding 2.5-3.5 g of potassium hexafluorophosphate, reacting for 5-6 h at 30-40 ℃, extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, and performing rotary evaporation, and passing through a silica gel column by using a dichloromethane and methanol mixed solution with a volume ratio of 300:1 to obtain orange yellow powder;
step 5, adding the orange powder prepared in the step 4 and 4-pyridinepinacol borate according to a molar ratio of 1: 3-5 into 35-45 mL of a mixed solvent of tetrahydrofuran and a potassium carbonate aqueous solution with a volume ratio of 2:1, introducing argon, adding 60-120 mg of tetratriphenyl phosphorodiamidate, reacting at 85-95 ℃ for 22-24 h, extracting with dichloromethane and saturated saline water after the reaction is finished, drying, filtering, and performing rotary evaporation, and passing the mixed solution of dichloromethane and methanol with a volume ratio of 100:1 through a silica gel column to obtain the orange powder, namely the metal-based ligand Ir (III) complex L with left-handed spiral chirality2；
Step 6, preparing the left-handed helical chiral metal-based ligand Ir (III) complex prepared in the step 5L2Adding the transition metal Cu salt and the transition metal Cu salt into 12-17 mL of acetonitrile solvent according to a molar ratio of 1: 2-4, stirring for 3-6 h at room temperature, filtering, standing the filtrate at room temperature for 3 weeks, and precipitating a green solid in the solution to obtain the target compound Cu-L2。
2. The compound Cu-L produced by the production method according to claim 11Or Cu-L2The application in catalyzing asymmetric oxidative dehydrogenation coupling (CDC) reaction of N-phenyltetrahydroisoquinoline and phenylacetylene molecules.
CN202010050378.8A 2020-01-14 2020-01-14 Preparation method and application of metal-organic framework structure compound with chiral pore structure Pending CN111116677A (en)

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CN112403525A (en) * 2020-12-03 2021-02-26 大连理工大学 Preparation method and application of metal organic framework catalyst with ligand molecule internal and external structures
CN113307769A (en) * 2021-05-17 2021-08-27 长江师范学院 1-alkynyl tetrahydroisoquinoline compound and preparation method thereof
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CN112264101A (en) * 2020-10-23 2021-01-26 大连理工大学 Preparation method and application of metal organic framework catalyst with torsion structure
CN112264101B (en) * 2020-10-23 2021-12-31 大连理工大学 Preparation method and application of metal organic framework catalyst with torsion structure
CN112403525A (en) * 2020-12-03 2021-02-26 大连理工大学 Preparation method and application of metal organic framework catalyst with ligand molecule internal and external structures
CN113307769A (en) * 2021-05-17 2021-08-27 长江师范学院 1-alkynyl tetrahydroisoquinoline compound and preparation method thereof
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CN113651855A (en) * 2021-08-19 2021-11-16 东北师范大学 Novel loaded crystalline porous framework material and preparation method and application thereof
CN113651855B (en) * 2021-08-19 2023-08-22 东北师范大学 Novel crystalline porous framework material, and preparation method and application thereof
CN114516891A (en) * 2022-01-16 2022-05-20 大连理工大学 Chiral binuclear Ir (III) metal-organic double helix structure compound and preparation method thereof

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