CN109265464B - Chiral covalent organic framework material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a chiral covalent organic framework material, which can be obtained by reacting a chiral monomer with 1,3, 5-tri (4-aminophenyl) benzene in an organic solvent under the catalysis of acetic acid; the structural formula of the chiral monomer is as follows:
or
Description
Technical Field
The invention relates to a chiral covalent organic framework material and a preparation method and application thereof.
Background
Chirality is one of the basic attributes of nature, and is related to life relatives, so that the study of chirality has important significance for the origin of life and human life. The enantiomers of chiral substances have the same physical properties, but differ in physiological and pharmacological activities, and have even opposite effects, so that it is important to obtain a chiral pure compound. Chiral separation, chiral resolution and chiral catalysis are the main approaches to obtain chiral compounds. These methods all require chirality as an induction to efficiently obtain chiral compounds. The homogeneous chiral compound inducing system has the disadvantages of large dosage, difficult separation from products and the like, so that the wide application of the small molecular chiral compound in industry is limited. To solve these problems, chiral porous materials have been produced.
The chiral porous material is an important chiral material, and has the characteristic of porosity, so the chiral porous material has wide application in the fields of chiral separation, chiral resolution and chiral catalysis. In recent years, chiral porous materials mainly include chiral high molecular polymer materials, chiral molecular sieve materials, chiral Metal Organic Framework (MOFs) materials, and chiral Covalent Organic Framework (COFs) materials. Compared with high molecular polymer materials, the COFs material has a regular pore channel structure; compared with molecular sieve materials, the structure of the COFs material is easy to adjust; compared with MOFs, the COFs material has better stability. However, the development and industrial application of chiral COFs materials are hindered by the few kinds of chiral COFs materials and the difficulty in synthesis.
Disclosure of Invention
The invention aims to provide a novel chiral covalent organic framework material.
In order to solve the technical problems, the invention provides the following technical scheme:
a chiral covalent organic framework material having the following structural units:
alternatively, the first and second electrodes may be,
wherein R is a group containing chiral carbon atoms, and R' is C1-C5 alkyl, benzyl or aryl. Aryl is phenyl or phenyl with at least one substituent on the phenyl ring.
Preferably, the group containing a chiral carbon atom is selected from
The preparation method of the chiral covalent organic framework material comprises the following steps:
under the catalysis of acetic acid, chiral monomers react with 1,3, 5-tri (4-aminophenyl) benzene in an organic solvent to obtain the chiral covalent organic framework material;
the structural formula of the chiral monomer is as follows:
wherein R is a group containing chiral carbon atoms, and R' is C1-C5 alkyl, benzyl or aryl.
Preferably, the organic solvent is one or more of 1, 4-dioxane, ethanol, chloroform, mesitylene, o-dichlorobenzene and n-butanol.
Preferably, the reaction temperature is 80-150 ℃ and the reaction time is 1-5 days.
Preferably, the total concentration of the chiral monomer and the 1,3, 5-tri (4-aminophenyl) benzene is 10-200mg/ml, and the molar amount of the 1,3, 5-tri (4-aminophenyl) benzene is 0.5-30 times, preferably 0.8-1 time of that of the chiral monomer; the molar amount of the acetic acid is 0.5-30 times, preferably 8-10 times of that of the chiral monomer.
The chiral covalent organic framework material is used as a catalyst for catalyzing the asymmetric ammoniation reaction of beta-ketoester.
Preferably, the beta-ketoester has the structural formula
Wherein R is1、R2、R3Each independently is C1-C5 alkyl, benzyl or aryl, or R1And R2And (4) cyclization.
A method for asymmetric ammoniation of a beta-ketoester, comprising: the beta-ketoester reacts with the azo compound under the catalysis of a catalytic amount of the chiral covalent organic framework material to obtain an asymmetric ammoniated product, wherein,
the structural formula of the beta-ketoester is shown as
The structural formula of the azo compound is
The structural formula of the asymmetric ammoniated product is shown as
R1、R2、R3Each independently is C1-C5 alkyl, benzyl or aryl, or R1And R2Cyclization;
R4and R5Is an amino protecting group, R4And R5The same or different.
The nitrogen-based protecting group may be selected from: benzyloxycarbonyl (Cbz), t-butoxycarbonyl (Boc), fluorenylmethyloxycarbonyl (Fmoc), allyloxycarbonyl (Alloc), trimethylsilyloxycarbonyl (Teoc), methoxycarbonyl, ethoxycarbonyl, p-toluenesulfonyl (Tos), trifluoroacetyl (Tfa), pivaloyl, benzyl (Bn), trityl (Trt), p-methoxybenzyl (PMB), 2, 4-dimethoxybenzyl (Dmb) and the like.
The preparation method of the chiral monomer comprises the following steps:
under the action of alkali and palladium catalyst, the precursor compound of the chiral monomer and p-formylphenylboronic acid undergo Suzuki coupling reaction to obtain the chiral monomer,
the precursor compound is
Wherein R is a group containing chiral carbon atoms, and R' is C1-C5 alkyl, benzyl or aryl.
Preferably, the base is potassium carbonate and the palladium catalyst is tetrakis (triphenylphosphine) palladium.
Preferably, the molar amount of the potassium carbonate is 1-20 times that of the precursor compound, the molar amount of the tetrakis (triphenylphosphine) palladium is 1-100% that of the precursor compound, and the molar ratio of the precursor compound to the p-formylphenylboronic acid is 1: 1-1: 20; more preferably, the molar amount of the potassium carbonate is 2 times that of the precursor compound, the molar amount of the tetrakis (triphenylphosphine) palladium is 10% of the precursor compound, and the molar ratio of the precursor compound to the p-formylphenylboronic acid is 1: 2.
Preferably, the Suzuki coupling reaction is carried out in a mixed solvent of 1, 4-dioxane and water with the volume ratio of 50: 1-1: 1, the reaction temperature is 80-130 ℃, and the reaction time is 10-72 hours; more preferably, the volume ratio of the 1, 4-dioxane and the water is 1: 1, the reaction temperature is 100 ℃, and the reaction time is 18 h.
The preparation method of the precursor compound comprises the following steps:
under the action of alkali, 2-chloro-4, 7-dibromobenzimidazole reacts with H2N-R reaction to obtain
Or, under the action of alkali,
reacting with methylsulfonyl chloride to obtain the compound
Preferably, the base is triethylamine, N-diisopropylethylamine, triethylenediamine, DBU, or sodium carbonate.
Preferably, the 2-chloro-4, 7-dibromobenzimidazole is reacted with H2The molar ratio of N-R to alkali is 1: 0.5-10, the reaction temperature is 100 ℃ and 200 ℃, and the reaction time is 5-48 h; more preferably, the 2-chloro-4, 7-dibromobenzimidazole is reacted with H2The molar ratio of N-R to alkali is 1: 1, the reaction temperature is 120 ℃, and the reaction time is 5 hours.
The above-mentioned
The molar ratio of the raw materials to the methylsulfonyl chloride to the alkali is 1: 0.5-10, the reaction temperature is 0-100 ℃, and the reaction time is 5-48 h; more preferably, the
With methanesulfonyl chloride,The molar ratio of the base is 1: 1.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a scheme for the synthesis of chiral monomers of the present invention;
FIG. 2 is a single crystal structure of compounds 3e and 5e of the present invention;
FIG. 3 is a synthetic route for chiral covalent organic framework materials of the present invention;
FIG. 4 is a powder X-ray diffraction pattern of a chiral covalent organic framework material of the present invention;
FIG. 5 is a solid nuclear magnetic spectrum of a chiral covalent organic framework material of the present invention;
FIG. 6 is a Fourier infrared spectrum of a chiral covalent organic framework material of the present invention;
FIG. 7 is a nitrogen desorption isotherm of a chiral covalent organic framework material of the invention;
FIG. 8 is a pore size distribution curve for a chiral covalent organic framework material of the present invention;
FIG. 9 is a thermogravimetric analysis curve of a chiral covalent organic framework material of the present invention;
FIG. 10 is a high performance liquid chromatogram of the asymmetric amination reaction product of example 25.
FIG. 11 is a graph showing the recycling performance of chiral covalent organic framework materials of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
In the examples of the present invention, the structural formula of compound 3(a-h) is as follows:
in the examples of the present invention, the structural formula of compound 5(a-h) is as follows:
EXAMPLES 1-8 Synthesis of Compounds 3a-3g
Under room temperature conditions, compound 1 (2-chloro-4, 7-dibromobenzimidazole, 1.0eq) and compound 2 (H)2N-R, 1.0eq) was added to the autoclave, N-diisopropylethylamine (1.0eq) was added, argon was bubbled, the autoclave was tightened, the autoclave was placed in an oil bath at 120 ℃ for reaction, after 5h of reaction, cooled to room temperature, and separated by column chromatography (with petroleum ether: ethyl acetate 4: 1-1: 1 or dichloromethane: methanol 30: 1-5: 1(v/v) as eluent) to give the product as a solid.
Compound 3b was the product as a white solid, yield: 87 percent.1H NMR(400MHz，CD3OD)δ＝7.44(d，J＝ 7.2Hz，2H)，7.35-7.32(m，2H)，7.26-7.22(m，1H)，7.01(br s，2H)，5.16(dd，J＝7.2Hz，J＝ 3.2Hz，1H)，3.92(dd，J＝11.2Hz，J＝4.4Hz，1H)，3.84(dd，J＝11.2Hz，J＝7.2Hz，1H)；13C NMR(150MHz，DMSO-d6)δ＝155.6，142.5，141.3，133.2，128.1，127.4，126.8，123.6，122.6， 106.5，99.6，65.0，57.7.HRMS(ESI)：calcd.for[C15H13Br2N3O+H]+411.9478，found 411.9479.
Compound (I)3c is the product as a white solid, yield: 90 percent.1H NMR(400MHz，DMSO-d6)δ＝11.15(s， 1H)，7.32-7.26(m，4H)，7.20-7.16(m，1H)，7.00(br s，2H)，6.36(d，J＝8.4Hz，1H)，5.01(br s，1H)，4.08(dd，J＝18.8Hz，J＝12.4Hz，1H)，3.50(dd，J＝15.6Hz，J＝11.2Hz，2H)，2.94(dd， J＝13.6Hz，J＝6.4Hz，1H)，2.86(dd，J＝13.6Hz，J＝7.2Hz，1H)；13C NMR(100MHz， DMSO-d6)δ＝155.6，142.9，138.9，133.2，129.3，128.1，126.0，124.0，122.0，106.7，99.5，62.2， 55.5，36.8.HRMS(ESI)：calcd.for[C16H15Br2N3O+H]+425.9634，found 425.9631.
Compound 3d was the product as a white solid, yield: 86 percent.1H NMR(400MHz，DMSO-d6)δ＝11.31(s， 1H)，7.30-7.16(m，4H)，7.06(s，2H)，6.48(d，J＝8.8Hz，1H)，5.38(dd，J＝8.8Hz，J＝4.8Hz， 2H)，4.59(s，1H)，3.15(dd，J＝16.0Hz，J＝4.4Hz，1H)，2.86(d，J＝16.4Hz，1H)；13C NMR (100MHz，DMSO-d6)δ＝156.0，142.7，142.4，140.6，133.3，130.0，127.4，126.3，125.0，124.4， 124.2，122.0，106.8，99.4，71.8，59.8，39.7.HRMS(ESI)：calcd.for[C16H13Br2N3O+H]+ 423.9478，found 423.9479.
Compound 3f is a white solid product, which is producedRate: 90 percent.1H NMR(400MHz，DMSO-d6)δ＝6.98(s，2H)， 6.54(d，J＝6.4Hz，1H)，3.81-3.76(m，1H)，2.49-2.34(m，2H)，2.25(s，6H)，2.03-1.98(m， 1H)，0.92(d，J＝6.8Hz，6H)；13C NMR(100MHz，DMSO-d6)δ＝157.0，138.3，122.6，102.8， 61.1，55.2，45.2，30.2，18.5，17.4.HRMS(ESI)：calcd.for[C14H20Br2N4+H]+405.0107，found 405.0105.
Compound 3g was the product as a white solid, yield: 94 percent.1H NMR(400MHz，CDCl3)δ＝7.02(s，2H)， 3.83(dt，J＝10.8Hz，J＝4.0Hz，1H)，3.12-3.30(m，1H)，2.56-2.38(m，1H)，2.35(s，6H)，1.97-1.95(m，1H)，1.88-1.84(m，1H)，1.74(d，J＝12.8Hz，1H)，1.50-1.34(m，5H)；13C NMR(100MHz，DMSO-d6)δ＝155.6，137.9，123.1，103.1，66.6，52.1，32.6，24.2，24.1，22.3. HRMS(ESI)：calcd.for[C15H20Br2N4+H]+417.0107，found 417.0103.
EXAMPLE 8 Synthesis of Compound 3h
In an ice water bath, triethylamine (1.0eq) and methanesulfonyl chloride (1.0eq) were added dropwise in this order to a round bottom flask of compound 3a (1.0eq), and after completion of the addition, the reaction was carried out at this temperature for 0.5 to 1 hour to make the hydroxyl group easily removable, and then the flask was warmed to room temperature, methanol (1.0eq) and triethylamine (1.0eq) were added in this order, and after completion of the addition, the flask was placed in an oil bath at 55 ℃ to react for 12 hours, and then cooled to room temperature, extracted three times with dichloromethane, the organic phases were combined, washed with water three times, washed with saturated salt water, dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and then the mixture was separated by chromatography (using petroleum ether: ethyl acetate ═ 2: 1 as an eluent) to obtain a white solid product for 3 hours. Yield: 96 percent.1H NMR(400MHz，DMSO-d6) δ＝7.81(s，1H)，7.06(d，J＝8.4Hz，1H)，6.95(d，J＝8.4Hz，1H)，4.42(t，J＝9.6Hz，1H)， 4.17(t，J＝8.0Hz，1H)，4.06(t，J＝8.0Hz，1H)，0.92(s，9H)；13C NMR(100MHz，DMSO-d6) δ＝162.4，147.4，131.2，124.1，122.5，107.1，98.9，69.4，44.6，33.5，25.0.HRMS(ESI)：calcd. for[C13H15Br2N3+H]+375.9665，found 375.9662.
Examples 9-16 Synthesis of Compounds 5a-5h
To a round bottom flask containing compound 3(1.0eq), p-formylphenylboronic acid 4(2.0eq), potassium carbonate (2.0eq) and tetrakis (triphenylphosphine) palladium (0.1eq) under argon atmosphere was added degassed 1, 4-dioxane/water 1/1(v/v) solvent, the mixture was allowed to react in an oil bath at 100 ℃ for 18 hours, then cooled to room temperature, extracted three times with dichloromethane, the organic phases were combined, washed three times with water, washed with saturated brine, dried over anhydrous sodium sulfate, evaporated under reduced pressure to remove the solvent, and separated by column chromatography (eluting with petroleum ether/ethyl acetate 2: 1-1: 2 or dichloromethane/methanol 50: 1-5: 1 (v/v)) to give a yellow solid product.
Compound 5b was the product as a yellow solid, yield: 75 percent.1H NMR(400MHz，DMSO-d6)δ＝11.02(s， 1H)，10.10(s，1H)，10.04(s，1H)，8.33(d，J＝8.0Hz，2H)，8.07(d，J＝8.4Hz，2H)，7.94(d，J＝ 8.4Hz，2H)，7.87(d，J＝8.0Hz，2H)，7.47-7.44(m，3H)，7.35(t，J＝7.6Hz，2H)，7.24(t，J＝ 7.2Hz，1H)，7.15(d，J＝8.0Hz，1H)，6.79(d，J＝7.2Hz，1H)，5.16(t，J＝5.2Hz，2H)，4.99 (dd，J＝12.0Hz，J＝6.4Hz，1H)，3.82-3.71(m，1H)；13C NMR(100MHz，DMSO-d6)δ＝ 192.6，192.6，156.2，144.5，144.1，142.3，141.9，135.0，134.2，131.8，130.2，129.3，128.7，128.3， 128.0，127.0，126.8，124.5，121.4，120.3，119.2，64.9，58.3.HRMS(ESI)：calcd.for [C29H23N3O3+H]+462.1812，found 462.1807.
Compound 5c was the product as a yellow solid, yield: 74 percent.1H NMR(400MHz，DMSO-d6)δ＝11.96(s， 1H)，10.10(s，1H)，10.07(s，1H)，8.46(d，J＝8.4Hz，2H)，8.07(d，J＝8.0Hz，2H)，8.00(d，J＝ 8.4Hz，2H)，7.87(d，J＝8.0Hz，2H)，7.47(d，J＝8.0Hz，1H)，7.37-7.28(m，4H)，7.21-7.16 (m，2H)，6.21(d，J＝8.0Hz，1H)，5.06(t，J＝4.8Hz，1H)，4.05(d，J＝6.4Hz，1H)，3.53(t，J＝ 6.4Hz，2H)，3.02(dd，J＝13.2Hz，J＝6.4Hz，1H)，2.90(dd，J＝13.2Hz，J＝7.2Hz，1H)；13C NMR(100MHz，DMSO-d6)δ＝192.6，156.3，144.8，144.2，142.5，139.2，134.9，134.3，131.8， 130.2，129.3，128.9，128.3，128.2，126.0，124.6，121.3，120.3，119.1，61.7，55.9，36.9.HRMS (ESI)：calcd.for[C30H25N3O3+H]+476.1969，found 476.1965.
Compound 5d was the product as a yellow solid, yield: 78 percent.1H NMR(400MHz，DMSO-d6)δ＝11.19(s， 1H)，10.10(s，1H)，10.01(s，1H)，8.44(d，J＝8.0 Hz，2H)，8.08(d，J＝8.0 Hz，2H)，7.96(d，J＝8.0Hz，2H)，7.91(d，J＝8.0Hz，2H)，7.49(d，J＝8.4Hz，1H)，7.36(d，J＝6.8Hz，1H)， 7.28-7.15(m，4H)，6.46(d，J＝8.4Hz，1H)，5.41-5.38(m，1H)，4.60(d，J＝4.4Hz，2H)，3.15 (dd，J＝16.4Hz，J＝4.8Hz，1H)，2.86(d，J＝16.4Hz，1H)；13C NMR(150MHz，DMSO-d6)δ＝192.7，192.6，156.9，144.8，144.2，143.0，142.4，140.6，135.0，134.2，132.0，131.3，130.2， 129.4，128.9，128.4，127.4，126.4，125.0，124.8，124.3，121.3，120.5，119.1，71.9，59.8，39.8. HRMS(ESI)：calcd.for[C30H23N3O3+H]+474.1812，found 474.1807.
Compound 5e was the product as a yellow solid, yield: 75 percent.1H NMR(400MHz，CDCl3)δ＝10.85(s，1H)， 10.07(s，1H)，10.03(s，1H)，8.55(br s，1H)，8.27(d，J＝7.2Hz，2H)，7.99(d，J＝8.0Hz，4H)， 7.85(d，J＝6.8Hz，2H)，7.37(d，J＝7.6Hz，1H)，7.10(d，J＝7.6Hz，1H)，3.37(br s，1H)，3.19 (br s，2H)，2.90(br s，1H)，1.88(br s，1H)，1.54(br s，1H)，1.40(br s，2H)，1.22(s，9H)，1.08(br s，1H)；13C NMR(100MHz，CDCl3)δ＝192.1，191.8，157.2，155.4，145.6，144.9，142.1，135.0， 134.6，132.0，130.5，129.9，129.4，128.9，125.8，123.1，121.6，119.9，80.2，57.2，46.4，45.6，29.2， 28.0，23.2.HRMS(ESI)：calcd.for[C31H32N4O4+H]+525.2491，found 525.2496.
Compound 5f is a yellow solid product, yield: 76 percent.1H NMR(400MHz，DMSO-d6)δ＝11.45(s，1H)， 10.06(s，2H)，8.41(br s，2H)，8.01(br s，6H)，7.27(br s，2H)，6.22(d，J＝5.6Hz，1H)，3.83(s， 1H)，2.43(dd，J＝12.0Hz，J＝8.0Hz，1H)，2.32(dd，J＝12.8Hz，J＝5.2Hz，1H)，2.18(s，6H)， 2.10(dd，J＝10.8Hz，J＝6.4Hz，1H)，0.95-0.92(m，6H)；13C NMR(100MHz，DMSO-d6)δ＝192.5，157.5，144.5，134.5，129.7，128.5，119.4，61.2，55.1，45.3，29.8，18.8，17.2.HRMS (ESI)：calcd.for[C28H30N4O2+H]+455.2442，found 455.2440.
Compound 5g was the product as a yellow solid, yield: 70 percent.1H NMR(400MHz，CDCl3)δ＝10.05(s，2H)， 8.03-7.96(m，8H)，7.30(s，2H)，3.40-3.34(m，1H)，2.48-2.38(m，3H)，2.23(s，6H)，1.98-1.76 (m，3H)，1.33-1.23(m，5H)；13C NMR(100MHz，CDCl3)δ＝191.9，157.1，145.1，136.9， 134.6，130.0，128.8，124.4，120.6，68.4，54.2，40.2，33.2，24.6，24.3，21.8.HRMS(ESI)：calcd. for[C29H30N4O2+H]+467.2442，found 467.2437.
Compound 5h was the product as a yellow solid, yield: 71 percent.1H NMR(400MHz，DMSO-d6)δ＝10.10(s， 1H)，10.04(s，1H)，8.35(d，J＝8.4Hz，2H)，8.06(d，J＝8.0Hz，2H)，7.98(d，J＝8.4Hz，2H)， 7.79(d，J＝8.4Hz，2H)，7.74(d，J＝1.6Hz，1H)，7.45(d，J＝8.4Hz，1H)，7.05(d，J＝8.0Hz， 1H)，4.08(t，J＝9.2Hz，1H)，3.83(t，J＝9.6Hz，1H)，3.57(dd，J＝8.0Hz，J＝10.0Hz，1H)， 0.86(s，9H)；13C NMR(100MHz，DMSO-d6)δ＝192.8，192.6，163.4，163.3，147.0，144.5， 143.6，135.0，134.3，133.2，132.0，132.0，131.5，131.4，130.5，129.7，130.5，129.7，129.5，129.3， 128.8，128.6，69.3，45.7，33.4，25.0.HRMS(ESI)：calcd.for[C27H25N3O2+H]+424.2020， found 424.2021.
Examples 17-24 Synthesis of chiral covalent organic framework materials
Compound 5(0.030mmol) and 1,3, 5-tris (4-aminophenyl) benzene (8.4mg, 0.024mmol) were charged to a glass ampoule. Then 0.1mL of ethanol and 0.1mL of mesitylene were added in sequence, the solution was dispersed uniformly by sonication for 20min in ultrasonic waves, and then 0.1mL of 3M HOAc solution was added. After the addition, the system was frozen with liquid nitrogen and the bottle neck was sealed after evacuation. And (3) heating the system to room temperature, putting the system into an oven at 120 ℃ for reaction for 3d, taking the system out of the oven after the reaction is finished, carefully breaking the bottleneck, transferring the generated solid into a centrifuge tube, washing the solid with tetrahydrofuran and acetone solvents for three times respectively, and naturally drying to obtain a yellow solid product, namely the chiral covalent organic framework material.
By comparing the powder X-ray diffraction pattern of the chiral material (as shown in FIG. 4), it can be known that: the chiral crystal materials have similar skeleton structures, and further can be known from a nitrogen adsorption and desorption curve and a pore size distribution curve (shown in fig. 7 and 8), and have certain specific surface area and similar regular pore channel structures.
From the solid nuclear magnetic spectrum (as shown in fig. 5) of the chiral material, it can be seen that benzene ring regions of the chiral material have similar peaks, while peaks of fat regions indicate that the chiral units are built into the chiral material, and these characterizations indicate that the material has similar structure, but the chiral structural units are different.
FIG. 9 is a thermogravimetric plot of a material illustrating the material's certain thermal stability.
Example 25 testing of catalytic Performance of chiral covalent organic framework materials of the invention on asymmetric beta-ketoester amination reactions
TAH-CCOF2(28.2mg, 0.04mmol) and β -ketoester compound 6(38.0mg, 0.20mmol) were added to a reaction tube, dichloromethane solvent (1.0mL) was added, and stirring was carried out at-78 ℃ for 20 min. Di-tert-butyl azodicarboxylate 7(50.6mg, 0.22mmol) was then added and the reaction stirred at-78 ℃ for 1 h. After the reaction, the reaction mixture was centrifuged to collect a liquid, the solvent was removed under reduced pressure, and the residue was purified by column chromatography (petroleum ether: ethyl acetate: 8: 1) to obtain the objective compound 8 in 98% yield and 84% ee (as measured by high performance liquid chromatography).
From the results of high performance liquid chromatography (as shown in fig. 10, chromatographic conditions: Daicel chiral AD-H column, 254nm, mobile phase hexane/i-PrOH ═ 90/10, flow rate 1.0mL/min), it was found that the chiral COFs material TAH-CCOF2 had relatively good enantioselectivity for the above asymmetric amination reaction (t (major) 18.4min, t (minor) 26.9 min).
The centrifuged or filtered TAH-CCOF2 is washed with tetrahydrofuran, dried and reused for catalyzing the reaction.
Fig. 11 is an X-ray diffraction pattern of TAH-CCOF2 after repeated use, and it can be seen that a crystal structure of TAH-CCOF2 is maintained to some extent after five catalytic uses, indicating that it has good recycling performance.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A chiral covalent organic framework material having the following structural units:
alternatively, the first and second electrodes may be,
wherein R is a group containing chiral carbon atoms, and R' is C1-C5 alkyl or benzyl;
the group containing a chiral carbon atom is selected from
2. A method of preparing the chiral covalent organic framework material of claim 1, comprising:
under the catalysis of acetic acid, chiral monomers react with 1,3, 5-tri (4-aminophenyl) benzene in an organic solvent to obtain the chiral covalent organic framework material;
the structural formula of the chiral monomer is as follows:
wherein R is a group containing chiral carbon atoms, and R' is C1-C5 alkyl or benzyl.
3. The method of claim 2, wherein: the organic solvent is one or more of 1, 4-dioxane, ethanol, chloroform, mesitylene, o-dichlorobenzene and n-butanol.
4. The method of claim 2, wherein: the reaction temperature is 80-150 ℃ and the reaction time is 1-5 days.
5. The production method according to any one of claims 2 to 4, characterized in that: the total concentration of the chiral monomer and 1,3, 5-tri (4-aminophenyl) benzene is 10-200mg/ml, the molar amount of the 1,3, 5-tri (4-aminophenyl) benzene is 0.5-30 times of that of the chiral monomer, and the molar amount of the acetic acid is 0.5-30 times of that of the chiral monomer.
6. Use of a chiral covalent organic framework material according to claim 1, characterized in that: the chiral covalent organic framework material is applied to catalyzing asymmetric ammoniation reaction of beta-ketoester as a catalyst.
7. Use according to claim 6, characterized in that: the structural formula of the beta-ketoester is shown as
Wherein R is1、R2、R3Each independently is C1-C5 alkyl or benzyl, or R1And R2And (4) cyclization.
8. A method for asymmetric ammoniation of a beta-ketoester, comprising: reacting a beta-ketoester with an azo compound catalyzed by a catalytic amount of a chiral covalent organic framework material of claim 1 to obtain an asymmetrically aminated product,
the structural formula of the beta-ketoester is shown as
The structural formula of the azo compound is
The structural formula of the asymmetric ammoniated product is shown as
R1、R2、R3Each independently is C1-C5 alkyl or benzyl, or R1And R2Cyclization;
R4and R5Is an amino protecting group, R4And R5The same or different.
9. The method of claim 8, wherein: the amino protecting group is selected from: benzyloxycarbonyl, t-butoxycarbonyl, fluorenylmethyloxycarbonyl, allyloxycarbonyl, trimethylsiloxyethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, p-toluenesulfonyl, trifluoroacetyl, pivaloyl, benzyl, trityl, p-methoxybenzyl and 2, 4-dimethoxybenzyl.
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