CN113185439B - V-shaped chiral carboxylic acid ligand, preparation method and application thereof - Google Patents

V-shaped chiral carboxylic acid ligand, preparation method and application thereof Download PDF

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CN113185439B
CN113185439B CN202110512295.0A CN202110512295A CN113185439B CN 113185439 B CN113185439 B CN 113185439B CN 202110512295 A CN202110512295 A CN 202110512295A CN 113185439 B CN113185439 B CN 113185439B
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cadmium
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carboxylic acid
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CN113185439A (en
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邓宁
石祥
赵亚玲
朱成峰
吴祥
付延明
李有桂
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Hefei University of Technology
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

The invention discloses a V-shaped chiral carboxylic acid ligand L-H 2 Relates to the technical field of synthetic chemistry and coordination chemistry, and has the following structural formula:the invention also provides a preparation method of the ligand and application of the ligand in the aspect of assembling chiral complexes. The invention has the beneficial effects that: the V-shaped chiral carboxylic acid ligand prepared by the invention has the advantages of cheap synthetic raw materials, simple preparation method, large-scale preparation, proper ligand rigidity and special coordination guidance, and is beneficial to overcoming the flexibility of the skeleton of the amino acid and the flexibility of the coordination mode, thereby being easy to assemble the complex material with chiral structure.

Description

V-shaped chiral carboxylic acid ligand, preparation method and application thereof
Technical Field
The invention relates to the technical field of synthetic chemistry and coordination chemistry, in particular to a V-shaped chiral carboxylic acid ligand, a preparation method and application thereof.
Background
The complex is a crystalline compound with specific structure and function formed by coordination of organic functional ligands containing electron donors such as oxygen, nitrogen and the like and metal ions. The structure of the compounds can be characterized by an X-ray single crystal diffraction technology, so that the compounds have definite structures and topologies; in addition, the complex can carry out fine design and regulation on the structure and function of the complex by means of regulating and controlling the structure of an organic ligand, the type of metal ions, crystallization conditions and the like, so that the complex becomes a research hot spot in the fields of chemistry, materials, information and medicine. The chiral complex has the functions of asymmetric catalysis and chiral separation because of being endowed with a unique chiral environment, and has great application prospect in the aspects of chiral compounds and chiral drug synthesis.
The most effective and direct means for preparing chiral complexes at present is to obtain the chiral complex by utilizing optically pure chiral ligands and metal ions through solvothermal reaction, but the synthesis cost of the chiral ligands is high, the control and assembly of the chiral complexes are difficult and other factors seriously restrict the synthesis of the chiral complexes and the development of functions of the chiral complexes. For this reason, researchers have spent a lot of effort over the last decade to design and synthesize a variety of chiral ligands with specific modes of attachment and rigid conjugated systems in order to achieve regulation of chiral complex structure and performance, but still face significant challenges. In view of the wide existence of optically pure natural amino acids in nature, the wide variety and low price of the optically pure natural amino acids have become the preference for preparing chiral ligands, but the high flexibility of the framework and the relative variability of the coordination modes make the control and assembly of chiral complexes difficult, and chiral complex materials with potential asymmetric catalysis and separation functions are difficult to obtain.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a V-shaped chiral carboxylic acid ligand which can be applied to preparing chiral complexes, a preparation method of the ligand, a cadmium-based chiral complex adopting the ligand and a preparation method of the cadmium-based chiral complex.
The invention solves the technical problems by the following technical means:
v-shaped chiral carboxylic acid ligand L-H 2 The structural formula is as follows:
the beneficial effects are that: v-shaped carboxylic acid ligands L-H in the present invention 2 Chiral amino acid is inlaid on the molecular skeleton to generate chirality, so that the chiral ligand can be used for preparing a complex with a chiral structure; in addition, the chiral ligand has proper molecular rigidity and special coordination guidance, and is favorable for overcoming the difficulty of assembling chiral complex caused by the inherent flexible skeleton structure and flexible coordination mode of amino acid molecules.
The invention also provides a V-shaped chiral carboxylic acid ligand L-H 2 The preparation method of (2) comprises the following steps:
(1) Fully stirring and mixing 5-amino isophthalic acid, methanol and concentrated sulfuric acid, carrying out reflux reaction on the obtained mixed solution, and purifying to obtain 5-amino isophthalic acid dimethyl ester after the reaction is completed;
(2) Dissolving chiral source L-Boc-proline, isobutyl chloroformate, dimethyl 5-amino isophthalate and triethylamine in solvent to obtain a reaction mixture, reacting at room temperature, and purifying to obtain an intermediate L-Me 2 ；
(3) The mass ratio of the substances is 1: L-Me of 3 2 And LiOH.H 2 O is dissolved in a mixed solvent of tetrahydrofuran, methanol and water, the organic solvent is removed after the reaction mixture is reacted at room temperature, the pH value of the solution is regulated to 2, and the V-shaped chiral carboxylic acid ligand L-H is obtained after purification 2 。
Preferably, the mass ratio of the L-Boc-proline, isobutyl chloroformate, dimethyl 5-amino isophthalate and triethylamine is 16.5:20:16.5:20, and the solvent used is dichloromethane.
The beneficial effects are that: the V-shaped chiral ligand prepared by the invention can be obtained by using cheap and easily available 5-amino isophthalic acid and chiral amino acid through simple organic synthesis, is beneficial to reducing the preparation cost of the chiral ligand, and has the advantages of simple and convenient preparation method, strong operability and convenient large-scale preparation.
Preferably, the volume ratio of tetrahydrofuran, methanol and water is 4:4:1.
When L-Me 2 And LiOH.H 2 When the ratio of the amount of O substance is less than 1:3, the yield of the product is lowered, and when the ratio is increased, the yield is increased, but the cost is increased. Under the above conditions, the chiral ligand was obtained in a yield of up to 95%.
The invention also provides a cadmium-based chiral complex, which takes metal cadmium ions as metal nodes and the V-shaped chiral carboxylic acid ligand L-H 2 Is a chiral complex crystal with a three-dimensional supermolecular structure, which is formed by bridging units and coordination assembly with the assistance of 4,4' -bipyridine (bpy), and the molecular formula is [ Cd ] 2 L 2 (bpy)·(H 2 O) 4 ] n The structural formula of the cadmium-based chiral complex is as follows:
the molecular structure of the complex crystal is periodically arranged in three-dimensional space, and n in the structural formula is an integer.
The beneficial effects are that: the Boc-protected L-proline in the cadmium-based chiral complex is at the top of a rigid V-shaped structure organism, so that the difficulty in coordination assembly of the chiral complex caused by structural flexibility and coordination uncertainty of chiral amino acid is overcome, and the prepared chiral amino protected by the Boc group and amide which does not participate in coordination in the cadmium-based chiral complex structure are alternately directed to an open chiral pore canal and can serve as potential action sites of asymmetric catalysis or chiral recognition functions.
Preferably, the unit cell parameters of the single crystal structure of the cadmium-based chiral complex are as follows: the space group is P2 1 The unit cell parameters areα＝γ＝90°,β＝105.658(1)°,/>
The invention also provides a preparation method of the cadmium-based chiral complex, which comprises the following steps:
(1) Preparing a solvothermal reaction solution: ligand L-H 2 Adding an auxiliary ligand 4,4' -bipyridine and metal cadmium salt into a mixed solvent, and fully stirring and mixing at room temperature to obtain a solvothermal reaction solution;
(2) Crystallization reaction: and (3) reacting the solvothermal reaction solution prepared in the step (1) at the temperature of 60 ℃ to obtain colorless transparent blocky crystals, and then filtering, washing and drying to obtain the cadmium-based chiral complex.
The beneficial effects are that: the synthesis method of the cadmium-based chiral complex provided by the invention is simple, the condition is mild, a large number of repetitions can be realized, and the phase purity can be ensured to be unchanged.
Preferably, the metal cadmium salt is Cd (OAc) 2 ·2H 2 O。
Preferably, the ligand L-H 2 The ratio of the amounts of the substances of the auxiliary ligand 4,4' -bipyridine and the metal cadmium salt is 2:1:2.
Preferably, the mixed solvent comprises N, N '-dimethylformamide and water, and the volume ratio of the N, N' -dimethylformamide to the water is 1:1.
The invention has the advantages that: the V-shaped chiral ligand prepared by the invention can be obtained by using cheap and easily available 5-amino isophthalic acid and chiral amino acid through simple organic synthesis, is beneficial to reducing the preparation cost of the chiral ligand, and has the advantages of simple and convenient preparation method, strong operability and convenient large-scale preparation.
According to the invention, the L-proline protected by Boc is inlaid at the top of a rigid V-shaped structure organism through chemical modification, so that on one hand, the difficulty in coordination assembly of chiral complexes caused by structural flexibility and coordination uncertainty of chiral amino acids is overcome, and on the other hand, the prepared cadmium-based chiral complexes are simple in synthesis method, mild in condition and easy to repeat, and chiral amino protected by Boc and amide which does not participate in coordination in the structure are staggered and directed to an open chiral pore canal, so that an action site is provided for potential asymmetric catalysis or chiral recognition functions.
Drawings
FIG. 1 is a V-shaped chiral carboxylic acid ligand L-H in example 1 of the present invention 2 And a synthetic route pattern of a cadmium-based chiral complex thereof;
FIG. 2 is a V-shaped chiral carboxylic acid ligand L-H in example 1 of the present invention 2 Nuclear magnetic hydrogen spectrum of (2);
FIG. 3 is a schematic diagram showing the synthesis and structure of a cadmium-based chiral complex in example 2 of the present invention;
FIG. 4 is a PXRD pattern of a cadmium-based chiral complex according to example 2 of the present invention;
FIG. 5 is a molecular structure diagram of a single crystal of a cadmium-based chiral complex in example 2 of the present invention;
FIG. 6 is a ladder-like one-dimensional chain in the structure of the cadmium-based chiral complex of example 2 of the present invention;
FIG. 7 is a three-dimensional network supramolecular structure formed by hydrogen bonding of the chiral cadmium-based complex of example 2 of the present invention, wherein the hydrogen bonding is shown by dotted lines.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
V-shaped chiral carboxylic acid ligand L-H 2 The preparation method of (2) has a synthetic route shown in figure 1, and specifically comprises the following stepsThe steps are as follows:
1) The V-shaped precursor 5-aminoisophthalic acid (5.0 g,27.6 mmol) was dissolved in 150mL methanol, concentrated sulfuric acid (3.0 mL,17.0 mmol) was slowly added dropwise, and the reaction mixture was refluxed for 12 hours, and then stopped to be cooled to room temperature; then adding a small amount of water to dilute the concentrated sulfuric acid, decompressing and evaporating the methanol, and then regulating the pH value of the reaction mixed solution to 7 by using a saturated sodium carbonate solution; the precipitated white solid was filtered, washed with water and dried to give 5.37g of 5-aminotransferase dimethyl phthalate as an intermediate product in 93% yield.
2) L-Boc-proline (3.55 g,16.5 mmol) as a chiral source was dissolved in 100mL of methylene chloride, isobutyl chloroformate (2.85 mL,20.0 mmol), triethylamine (2.8 mL,20.0 mmol) and dimethyl 5-aminoisophthalate (3.45 g,16.5 mmol) were added respectively at 0℃and then reacted at room temperature for 12 hours. The reaction mixture was washed with a saturated potassium hydrogen sulfate solution, a saturated sodium hydrogen carbonate solution and brine in this order, and the crude product-containing organic phase was separated, dried and purified by column chromatography (petroleum ether: ethyl acetate=15:1) to give 6.3g of L-Me as a white solid 2 The yield was 86%.
3) L-Me 2 (4.06 g,10 mmol) and LiOH H 2 O (1.26 g,30 mmol) was dissolved in a mixed solvent of tetrahydrofuran (40 mL), methanol (40 mL) and water (10 mL), and the resulting reaction mixture was reacted at room temperature for 12 hours. Then, the organic solvent was distilled off, the pH of the solution was adjusted to 2 with dilute hydrochloric acid, and the organic phase was extracted with ethyl acetate and dried, concentrated to give 3.6g of a white chiral ligand L-H 2 The yield was 95%, the ligand was characterized by nuclear magnetic resonance hydrogen spectrum as the target product (fig. 2), and it was directly used for the preparation of chiral complex material.
Example 2
The preparation method of the cadmium-based chiral complex, the synthetic route of which is shown in figure 3, specifically comprises the following steps:
weighing the Cd (OAc) 2 ·2H 2 O(5.33mg，0.02mmol)、L-H 2 (8.3 mg,0.02 mmol), 4' -bipyridine (bpy) (1.56 mg,0.01 mmol) in DMF (0.5 mL) and H 2 O (0.5 mL) and sealing the mixture in explosion-proof glass, and heating at 60 ℃ for 48 hoursAfter that, the colorless transparent blocky crystal is obtained after cooling, and then 6.4mg of cadmium-based chiral complex is obtained after filtering, ethanol washing and natural air drying, repeated reaction is carried out for a plurality of times, and the obtained chiral complex is subjected to powder X-ray diffraction (PXRD) measurement, so that the result shows that the PXRD spectrogram obtained by the experiment is basically consistent with the PXRD spectrogram simulated by a single crystal structure, and the phase purity is better (figure 4).
Experimental data and analysis:
structure measurement of the single crystal of the cadmium-based chiral complex prepared in example 1:
the measuring method comprises the following steps:
picking up single crystal sample of complex with proper size, collecting diffraction data on BL17B line station of national protein science research (Shanghai) facility, and collecting diffraction data with incident light source with wavelength lambda ofThe single crystal diffraction data is reduced by APEX III software, single crystal structure analysis and refinement are carried out by Olex 2 software, and full matrix least squares (full-matrix least-squares refinement based on F) is adopted 2 ) Defining all non-hydrogen atoms and making anisotropic finishing treatment to obtain ligand L-H 2 And hydrogen atoms on bpy molecules are completed through theoretical hydrogenation.
Measurement results: the unit cell parameters of the single crystal of the cadmium-based complex of the invention are α＝γ＝90°,β＝105.658(1)°,/>
As can be seen from structural analysis of the single crystal of the complex, the single crystal of the complex is crystallized in chiral P2 1 Space group whose asymmetric unit contains 2 Cd whose crystal phases are independent 2+ Ions, 2 crystalline phase independent deprotonated L ligand molecules, 1 bpy molecule and 4 coordinated water molecules, as shown in FIG. 5, which is comparable to the formula [ Cd ] 2 L 2 (bpy)·(H 2 O) 4 ] n The same applies. Two Cds in the complex structure 2+ The ions are in distorted tetragonal cone coordination configuration, the equatorial plane of the ion is occupied by 2 single-tooth carboxyl oxygen atoms, 1 pyridine nitrogen atom and 1 coordination water molecule from 2 ligands, the vertex position of the ion is occupied by another 1 coordination water molecule, and the generated CdO 4 The length of Cd-O bond in N cluster ranges from 1.9522 (4) toThe bond lengths of Cd1-N5 and Cd2-N6 are respectivelyAs shown in FIG. 6, each CdO in the complex 4 The N cluster is bridged and coordinated by 2 ligand L and 1 bpy molecule respectively to generate a ligand with 2 1 One-dimensional chains of ladder-like structures of helical features; in addition, the ladder-shaped one-dimensional chains are further assembled into a three-dimensional porous supermolecular structure through strong hydrogen bonding between coordinated water molecules and carboxyl oxygen atoms, and the Boc-protected chiral amino units and amide groups which do not participate in coordination are staggered and directed to chiral channels in a single crystal structure (figure 7), so that potential action sites for asymmetric catalysis or chiral recognition functions are generated.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. A first partA cadmium-based chiral complex characterized in that: the cadmium-based chiral complex takes metal cadmium ions as metal nodes and adopts V-shaped chiral carboxylic acid ligand L-H 2 Is a chiral complex crystal with a three-dimensional supermolecular structure, which is formed by bridging units and coordination assembly with the assistance of 4,4' -bipyridine (bpy), and the molecular formula is [ Cd ] 2 L 2 (bpy)·(H 2 O) 4 ] n The structural formula of the cadmium-based chiral complex is as follows:
wherein n is an integer; v-shaped chiral carboxylic acid ligand L-H 2 The structural formula is as follows: />The unit cell parameters of the single crystal structure of the cadmium-based chiral complex are as follows: the space group is P2 1 The unit cell parameters are-> α＝γ＝90°,β＝105.658(1)°,/>
2. The cadmium-based chiral complex of claim 1, wherein: the V-shaped chiral carboxylic acid ligand L-H 2 The preparation method of (2) comprises the following steps:
(1) Fully stirring and mixing 5-amino isophthalic acid, methanol and concentrated sulfuric acid, carrying out reflux reaction on the obtained mixed solution, and purifying to obtain 5-amino isophthalic acid dimethyl ester after the reaction is completed;
(2) Reaction prepared by dissolving chiral source L-Boc-proline, isobutyl chloroformate, dimethyl 5-amino isophthalic acid and triethylamine in solventThe mixture is reacted at room temperature, and after the reaction is completed, the intermediate product L-Me is obtained by purification 2 ；
(3) The mass ratio of the substances is 1: L-Me of 3 2 And LiOH.H 2 O is dissolved in a mixed solvent of tetrahydrofuran, methanol and water, the organic solvent is removed after the reaction mixture is reacted at room temperature, the pH value of the solution is regulated to 2, and the V-shaped chiral carboxylic acid ligand L-H is obtained after purification 2 。
3. The cadmium-based chiral complex of claim 2, wherein: the mass ratio of the L-Boc-proline to the isobutyl chloroformate to the 5-dimethyl amino isophthalate to the triethylamine is 16.5:20:16.5:20, and the solvent used is dichloromethane.
4. A method for preparing the cadmium-based chiral complex according to claim 1, wherein: the method comprises the following steps:
(1) Preparing a solvothermal reaction solution: ligand L-H 2 Adding an auxiliary ligand 4,4' -bipyridine and metal cadmium salt into a mixed solvent, and fully stirring and mixing at room temperature to obtain a solvothermal reaction solution;
(2) Crystallization reaction: and (3) reacting the solvothermal reaction solution prepared in the step (1) at the temperature of 60 ℃ to obtain colorless transparent blocky crystals, and then filtering, washing and drying to obtain the cadmium-based chiral complex.
5. The method for preparing a cadmium-based chiral complex according to claim 4, wherein: the method comprises the following steps: the metal cadmium salt is Cd (OAc) 2 ·2H 2 O。
6. The method for preparing a cadmium-based chiral complex according to claim 4, wherein: the method comprises the following steps: the ligand L-H 2 The ratio of the amounts of the substances of the auxiliary ligand 4,4' -bipyridine and the metal cadmium salt is 2:1:2.
7. The method for preparing a cadmium-based chiral complex according to claim 4, wherein: the method comprises the following steps: the mixed solvent comprises N, N '-dimethylformamide and water, and the volume ratio of the N, N' -dimethylformamide to the water is 1:1.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
CN109503669A (en) * 2018-11-03 2019-03-22 桂林理工大学 5- 4,4 '-bipyridyl of amino isophthalic acid cobalt complex and preparation method

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Publication number Priority date Publication date Assignee Title
CN109503669A (en) * 2018-11-03 2019-03-22 桂林理工大学 5- 4,4 '-bipyridyl of amino isophthalic acid cobalt complex and preparation method

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