Flaky supramolecular chiral copper catalyst based on molecular self-assembly and application of flaky supramolecular chiral copper catalyst
By designing sheet-like supramolecular chiral copper catalysts, the problem of helical morphology dependence in existing technologies has been solved, realizing the application of efficient and easy-to-prepare non-helical chiral catalysts in asymmetric catalysis, and providing new design ideas and experimental basis.
Patent Information
- Application Number
- CN202511051390.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-29
- Publication Date
- 2025-11-21
AI Technical Summary
Existing chiral catalyst designs mostly rely on helical morphology, which leads to complex synthesis, high cost, and limited innovation. Traditional concepts have restricted the development of non-helical chiral catalysts.
A sheet-like supramolecular chiral copper catalyst based on molecular self-assembly was designed and synthesized. The sheet-like supramolecular chiral copper catalyst L-ThrC10-NS-Cu(Ⅱ) was formed by assembling L-ThrC10-20 with Cu2+ and applied to the asymmetric Diels-Alder reaction.
Achieving high yield and high enantioselectivity, the sheet-like supramolecular catalyst, independent of helical morphology, exhibited excellent catalytic performance in the Diels-Alder reaction, providing new design ideas and experimental basis.
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Figure CN120984332A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of asymmetric catalysis, and particularly relates to a sheet-like supramolecular chiral copper catalyst based on molecular self-assembly and application thereof in asymmetric Diels-Alder reaction. BACKGROUND
[0002] Asymmetric catalysis is one of the core technologies of modern synthetic chemistry, and its goal is to produce single chiral product (enantiomer) with high selectivity through chiral catalyst. Developing chiral catalysts with high efficiency, high selectivity, novel structure and easy preparation is the continuous pursuit of the field.
[0003] For a long time, the design of chiral catalysts is often closely related to specific three-dimensional chiral structures. Among them, "spiral morphology" is considered as a classic structure paradigm for efficient transmission and amplification of chirality. Whether it is a naturally occurring spiral structure (such as DNA, α-helix protein) or an artificially synthesized spiral molecule (such as helical ene, helical chiral ligand, helical metal complex), its inherent helical chirality can provide a clear and pre-organized chiral microenvironment. This spatially twisted structure is believed to effectively distinguish the enantiomeric faces or enantiomers of the reactants, thereby achieving high levels of asymmetric induction. Therefore, in the design of many efficient chiral catalysts, constructing a catalytically active center with a spiral structure has become a widely adopted and successful strategy.
[0004] Although spiral structure catalysts have achieved great success, their design and synthesis usually involve complex multi-step organic synthesis or precise metal coordination self-assembly processes, which may lead to high cost, complicated steps or stability challenges. In addition, the prevailing view that the spiral morphology of the catalyst is an almost "necessary condition" or "gold standard" for achieving efficient asymmetric catalysis may limit the diversity and innovation of chiral catalyst structure design to some extent. Therefore, exploring and verifying whether chiral structures with non-traditional morphology (especially non-spiral morphology) can also effectively achieve asymmetric catalysis not only has important theoretical significance, but also opens up new ways for developing new chiral catalysts with simpler structure, more convenient synthesis and excellent performance.
[0005] The development of supramolecular chemistry provides a new platform for chiral catalysis. Through self-assembly processes driven by non-covalent interactions (such as hydrogen bonding, π-π stacking, van der Waals forces, metal coordination, electrostatic interaction, etc.), chiral supramolecular assemblies with complex structures and dynamic adjustability can be constructed. Due to their easily controllable chiral microenvironment, synergistic effect and potential "self-repairing" ability, such assemblies have become a research hotspot in the field of chiral catalysis. However, most of the high-performance supramolecular chiral catalysts reported so far still tend to form "spiral structures" (such as helical strips, helical tubes, etc.) to utilize the inherent spatial asymmetry of the spiral morphology.
[0006] Based on the above background, the inventors designed and synthesized a sheet-like supramolecular chiral catalyst, the core innovation of which is that it is significantly different from the traditional "non-helical morphology" feature. Although the invention does not have a typical helical twisted structure, the sheet-like supramolecular assembly exhibits excellent asymmetric catalytic performance, and high yield and high enantioselectivity can be obtained. This discovery has challenged the traditional concept that "efficient asymmetric catalysis depends on helical morphology", and proved that carefully designed layered chiral superstructure can also construct effective chiral cavities or interfaces to realize precise control of the stereochemistry of the reaction. The invention provides an important theoretical and practical basis for developing non-helical morphology chiral catalysts with novel structure, excellent performance and easy to scale up. The invention provides a new strategy for developing non-helical supramolecular chiral catalysts, which has important application value in the field of asymmetric synthesis. SUMMARY
[0007] The invention provides a sheet-like supramolecular chiral copper catalyst based on molecular self-assembly and its application in asymmetric Diels-Alder reaction. Compared with traditional helical supramolecular catalysts, the invention opens up a new system of non-helical supramolecular chiral catalysts, providing a new design idea for the field of asymmetric catalysis.
[0008] To achieve the above technical purpose, the technical scheme of the invention is: The invention provides a sheet-like supramolecular chiral copper catalyst based on molecular self-assembly, which is prepared by the following preparation method: 1) Dissolve L -ThrC 10-20 in a solvent and stir to obtain a methanol solution of L -ThrC 10-20 ; 2) Under the stirring state of step 1), add ultrapure water to the system, which immediately produces white suspensions. After stirring, sheet-like supramolecular assemblies L -ThrC 10-20 -NS are obtained; 3) Add Cu 2+ , and after stirring, sheet-like supramolecular chiral copper catalyst L -ThrC 10-20 -NS-Cu(II) is obtained.
[0009] In step 1), the concentration of L -ThrC 10-20 is 2mM-6mM.
[0010] In step 1), the dissolving operation is magnetic stirring dissolution or ultrasonic dissolution.
[0011] In step 1), the temperature during stirring is 15-35℃, and the stirring time is 1-10 min.
[0012] In step 1), the solvent is methanol, ethanol or isopropanol.
[0013] In steps 2) and 3), the stirring time is 1-10 min.
[0014] The Cu 2+ The amount of addition is L -ThrC 10-20 The amount of addition is 1-10% mol.
[0015] The application also provides application of the plate-shaped supramolecular chiral copper catalyst based on molecular self-assembly in asymmetric Diels-Alder reaction, which comprises the following steps: transferring the plate-shaped supramolecular chiral copper catalyst to 0℃, and adding reactants cyclopentadiene and chalcone derivatives to perform asymmetric catalytic Diels-Alder reaction.
[0016] Compared with the prior art, the application has the following beneficial effects: (1) The plate-shaped supramolecular chiral copper catalyst based on molecular self-assembly is successfully constructed for the first time. L -ThrC 16 Compared with Cu 2+ The plate-shaped supramolecular chiral copper catalyst based on molecular self-assembly L -ThrC 16 -NS-Cu(II) is constructed, which exhibits obvious enantioselectivity in Diels-Alder reaction and can efficiently catalyze the generation of S -endo configuration product (ee value is 45%).
[0017] (2) Through systematic structure-property relationship research, it is revealed that the stereoselectivity of the catalyst is derived from its unique plate-shaped supramolecular chiral microenvironment, and the ordered two-dimensional structure provides accurate spatial orientation control for the reaction substrate.
[0018] (3) Compared with the traditional helical supramolecular catalyst, the application opens up a new system of non-helical supramolecular chiral catalysts and provides a new design idea for the field of asymmetric catalysis.
[0019] (4) The research result not only provides a new strategy for developing efficient chiral catalysts, but also provides important experimental basis for deeply understanding the basic scientific problem of chiral induction and transmission mechanism through the correlation research between the structure of supramolecular assembly and the catalytic performance. BRIEF DESCRIPTION OF DRAWINGS
[0020] Figure 1 The figure is a process flowchart of the application.
[0021] Figure 2 yes L -ThrC 16 -NS (2a) L -ThrC 16 SEM image and schematic diagram of -NS-Cu(Ⅱ) (2b).
[0022] Figure 3 yes L -ThrC 16 XRD pattern of -NS-Cu(Ⅱ).
[0023] Figure 4 yes L -ThrC 16 -Cu(Ⅱ), L -ThrC 16 Comparison of the effects of -NS-Cu(Ⅱ) asymmetric catalysis on Diels-Alder reaction. Detailed Implementation
[0024] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0025] The process flow diagrams for Examples 1-3 are as follows: Figure 1 As shown. Example 1
[0026] This embodiment provides a sheet-like supramolecular chiral copper catalyst based on molecular self-assembly, which is prepared by the following method: 1) Take 14.3 mg of L -ThrC 16 First, dissolve the substance in 4 ml of methanol using magnetic stirring or ultrasonication. L -ThrC 16 The concentration was 4 mM), and the mixture was stirred at 25°C for 10 minutes to obtain the desired result. L -ThrC 16 A methanol solution; 2) Under the stirring state in step 1), add 6 ml of ultrapure water to the system. A white suspension will immediately form. After stirring for 10 min, a sheet-like supramolecular assembly is obtained. L -ThrC 16 -NS; 3) 1 μmol of Cu(NO3)2.3H2O was added, and after stirring for 1-10 min, a flaky supermolecular chiral copper catalyst was obtained L -ThrC 16 -NS-Cu(II). Example 2
[0027] This example provides a flaky supermolecular chiral copper catalyst based on molecular self-assembly, which is prepared by the following preparation method: 1) 16.5 mg of L -ThrC 10 was first dissolved by magnetic stirring or ultrasonic dissolution in ethanol L -ThrC 10 at a concentration of 6 mM, and stirred at a temperature of 15°C for 10 min to obtain a methanol solution of L -ThrC 10 2) Under the stirring condition of step 1), 6 ml of ultrapure water was added to the system, and white suspensions were immediately generated. After stirring for 1-10 min, a flaky supermolecular assembly L -ThrC 10 -NS was obtained. 3) 1 μmol of Cu(NO3)2.3H2O was added, and after stirring for 1-10 min, a flaky supermolecular chiral copper catalyst L -ThrC 10 -NS-Cu(II) was obtained. Example 3
[0028] This example provides a flaky supermolecular chiral copper catalyst based on molecular self-assembly, which is prepared by the following preparation method: 1) 8.3 mg of L -ThrC 20 was first dissolved by magnetic stirring or ultrasonic dissolution in isopropanol L -ThrC 20 at a concentration of 2 mM, and stirred at a temperature of 35°C for 1 min to obtain a methanol solution of L -ThrC 20 2) Under the stirring condition of step 1), 6 ml of ultrapure water was added to the system, and white suspensions were immediately generated. After stirring for 1 min, a flaky supermolecular assembly L -ThrC 20 -NS was obtained. 3) 1 μmol of Cu(NO3)2.3H2O was added, and after stirring for 1-10 min, a flaky supermolecular chiral copper catalyst L -ThrC20 -NS-Cu(Ⅱ).
[0029] Application Example The present embodiment provides application of the plate-like supramolecular chiral copper catalyst based on molecular self-assembly in asymmetric Diels-Alder reaction, including the following steps: The plate-like supramolecular chiral copper catalyst L -ThrC 16 -NS-Cu(Ⅱ) system was transferred to 0℃ and stirred, 0.05 mmol chalcone derivative (10.5 mg) was added, at this time the white suspension immediately changed into fluorescent green suspension, then 0.5 mmol second reactant cyclopentadiene (33.0 mg) was added to carry out asymmetric catalytic Diels-Alder reaction, after 6h reaction, the reaction product was purified, the yield was 91% and ee value was 45%.
[0030] Characterization: From FIG. 2(a) and 2(b), it can be seen that, L -ThrC 16 -NS and L -ThrC 16 -NS-Cu(Ⅱ) All showed nanosheet morphology, Cu 2+ The addition of Cu
[0031] Figure 3 For L -ThrC 16 -NS-Cu(Ⅱ) XRD spectrum of L -ThrC 16 -NS-Cu(Ⅱ) showed a layered structure, and the thickness was 2.98 nm.
[0032] FIG. 4 shows L -ThrC 16 -Cu(Ⅱ) had poor catalytic activity and selectivity effect on Diels-Alder reaction, while the plate-like supramolecular chiral copper catalyst greatly improved the catalytic activity and selectivity of Diels-Alder reaction.
[0033] Although the embodiments of the present application have been disclosed as above, it is not limited to the application listed in the specification and embodiments, and can be fully applied to various fields suitable for the present application, and other modifications can be easily realized by those skilled in the art, and therefore the present application is not limited to specific details and the figures shown and described herein, without departing from the general concept defined by the claims and equivalent scope.
Claims
1. A sheet-like supramolecular chiral copper catalyst based on molecular self-assembly, characterized in that... Prepared by the following method: 1) L -ThrC 10-20 First, dissolve it in a solvent and stir to obtain... L -ThrC 10-20 A methanol solution; 2) Under the stirring state in step 1), ultrapure water is added to the system. At this time, white suspension is immediately generated. After stirring, sheet-like supramolecular assemblies are obtained. L -ThrC 10-20 -NS; 3) Add Cu 2+ After stirring, a sheet-like supramolecular chiral copper catalyst was obtained. L -ThrC 10-20 -NS-Cu(Ⅱ).
2. The sheet-like supramolecular chiral copper catalyst based on molecular self-assembly according to claim 1, characterized in that: In step 1), the aforementioned L -ThrC 10-20 The concentration is 2mM-6mM.
3. The sheet-like supramolecular chiral copper catalyst based on molecular self-assembly according to claim 1, characterized in that: In step 1), the dissolution operation is magnetic stirring dissolution or ultrasonic dissolution.
4. The sheet-like supramolecular chiral copper catalyst based on molecular self-assembly according to claim 1, characterized in that: In step 1), the temperature during stirring is 15℃-35℃, and the stirring time is 1-10min.
5. The sheet-like supramolecular chiral copper catalyst based on molecular self-assembly according to claim 1, characterized in that: In step 1), the solvent is methanol, ethanol or isopropanol.
6. The sheet-like supramolecular chiral copper catalyst according to claim 1, characterized in that: In steps 2) and 3), the stirring time is 1-10 minutes.
7. The sheet-like supramolecular chiral copper catalyst according to claim 1, characterized in that: In step 3), the Cu 2+ The amount added is L -ThrC 10-20 The amount added is 1%mol-10%mol.
8. The application of the sheet-like supramolecular chiral copper catalyst based on molecular self-assembly as described in any one of claims 1-7 in the asymmetric Diels-Alder reaction, characterized in that... The process includes the following steps: transferring the sheet-like supramolecular chiral copper catalyst to 0°C, adding reactants cyclopentadiene and chalcone derivatives to carry out an asymmetric catalytic Diels-Alder reaction.