A binuclear alkali metal complex, its preparation method and application

Abstract

This invention discloses a binuclear alkali metal complex, its preparation method, and its application. The general formula of the binuclear alkali metal complex is M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is an organophosphate anion or a chiral phosphate anion. The binuclear alkali metal complex is a novel structurally stable polydentate alkali metal phosphate complex, which can be used as a catalytic system for alkyne cycloaddition / asymmetric 1,2-migration rearrangement reactions, solving the problem of catalyst poisoning in traditional transition metal catalytic systems, which prevents them from entering new catalytic cycles.

Description

Technical Field

[0001] This invention belongs to the field of metal complex technology, specifically, it relates to a binuclear alkali metal complex, its preparation method and application. Background Technology

[0002] The process by which a molecule or ion combines with a metal ion to form a very stable new ion is called a complexation reaction, also known as a coordination reaction. A compound composed of complexed ions or complexed molecules is called a complex. In a complex, the central ion is the core part, located at the center of the complex ion. It is generally a positively charged ion (most of which are metal ions), and the ions or molecules that are complexed with the central ion are called ligands.

[0003] Transition metals, with their numerous empty orbitals and suitable atomic radii, readily accept electrons from ligands to form stable complexes, playing a crucial role in asymmetric catalysis. For nearly half a century, the chiral ligand catalysis mode of transition metals has led to the rapid development of asymmetric organocatalysis, finding widespread application in organic synthesis reactions such as asymmetric hydrogenation, coupling reactions, and hydrocarbon activation. However, transition metals suffer from drawbacks including scarcity, high cost, and significant side effects on human health, particularly in the pharmaceutical industry where strict control of heavy metal residues is necessary, limiting their application. To address these issues, in recent years, the industry has gradually developed schemes using alkali metals to prepare complexes. Alkali metals offer advantages such as abundant reserves, low cost, and good biocompatibility. From the perspective of green chemistry and sustainable development, alkali metals are considered the most ideal substitute for transition metals in asymmetric catalysis.

[0004] In ideal asymmetric catalysis, metals and substrates reversibly bind or decouple through weak interactions, forming an asymmetric catalytic cycle. For substrates with strong complexing abilities, strong interactions with strong Lewis acids (transition metals) are common, leading to catalyst deactivation and halting the catalytic cycle. Conversely, weak Lewis acids (alkali metals) may be advantageous in catalyzing reactions with strongly coordinated substrates. Due to their unique atomic structure, alkali metals most commonly exist as monovalent metal cations after losing their outermost electrons. These cations are characterized by low electronegativity, low charge number, and large radius, making them typical weak Lewis acids. They struggle to form stable complexes with Lewis base ligands. Furthermore, alkali metal ions cannot provide sufficient empty orbitals for organic ligands, hindering the formation of stable, multidentate complexes with chiral ligands. Currently, apart from a few organic compounds such as crown ethers and phenols that can form stable complexes with alkali metals, other forms of chiral alkali metal complexes are rarely reported. In recent years, organophosphate compounds have gradually attracted widespread attention as metal ligands. Due to their unique phosphate functional groups, organophosphates possess distinctive coordination abilities: firstly, the carboxylic acid anion formed after deprotonation of organophosphates has a strong electron-donating ability, enabling it to form relatively stable coordinate bonds with metals. Secondly, the variability in the degree of deprotonation of carboxylic acids results in diverse coordination forms, but there are currently no reports of alkali metal organophosphate complexes.

[0005] In view of this, the research and development of a novel alkali metal organophosphate complex and its application in the field of asymmetric catalysis has become an urgent technical problem to be solved. Summary of the Invention

[0006] Therefore, the technical problem to be solved by the present invention is to fill the gap in the prior art by proposing a binuclear alkali metal complex and its preparation method and application.

[0007] To solve the above-mentioned technical problems, the technical solution of the present invention is as follows:

[0008] The first aspect of this invention provides a binuclear alkali metal complex, wherein the general formula of the binuclear alkali metal complex is M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is an organophosphate anion or a chiral phosphate anion. When L is an organophosphate anion, the general formula of L is: Alternatively, when L is a chiral organophosphate anion, the general formula of L is: In formula I, R 1 R 2 Selected from substituted aliphatic groups, substituted heteroaliphatic groups, substituted aryl groups, and substituted heteroaryl groups; in Formula II, * represents a chiral center.

[0009] Preferably, the general structural formula of the binuclear alkali metal complex is:

[0010]

[0011] n = x + y + z, where x, y, and z are selected from positive integers between 0 and 7.

[0012] Preferably, when L is a chiral organophosphate anion, L is any one of the following structural formulas III to IX:

[0013]

[0014]

[0015] In the above general formula, R 1 R 2 R 3 R 4 R 5 R 6 The atoms are selected from hydrogen, halogen, substituted aliphatic group, substituted heteroaliphatic group, substituted aryl group, and substituted heteroaryl group respectively; Y is any one of N, O, and S atoms; n is a positive integer between 0 and 7.

[0016] A second aspect of the present invention provides a method for preparing the aforementioned binuclear alkali metal complex, comprising the following steps:

[0017] S1. Dissolve the phosphate ligand LH in an organic solvent to obtain a phosphate ligand solution, wherein the phosphate ligand LH is an organic phosphate ligand or a chiral phosphate ligand;

[0018] S2. Add the alkali metal salt MnXn to the phosphate ligand solution, wherein the molar ratio of phosphate ligand to alkali metal salt is 1:2-5, to obtain a mixed reaction solution, wherein M is an alkali metal ion, X is an anion, and m and n are both positive integers.

[0019] S3. The mixed reaction solution is heated and stirred to react. The product is filtered and dried to obtain the binuclear alkali metal complex.

[0020] Preferably, X is any one of the following: halide ion, cyano ion, azide ion, bicarbonate ion, carbonate ion, nitrate ion, sulfate ion, sulfonate ion, oxalate ion, acetate ion, perchlorate ion, trifluoroacetate ion, trichloroacetate ion, trifluoromethanesulfonate ion, tetrafluoroborate ion, p-methylbenzoate ion, p-methylbenzenesulfonate ion, o-nitrophenoloxy, p-nitrophenoloxy, m-nitrophenoloxy, 2,4-dinitrophenoloxy, 3-5-dinitrophenoloxy, 2,4,6-trinitrophenoloxy, 3,5-dichlorophenoloxy, 3,5-difluorophenoloxy, 3,5-di-trifluoromethylphenoloxy, or pentafluorophenoloxy anion.

[0021] Preferably, the organic solvent is at least one selected from N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, toluene, methanol, ethanol, acetonitrile, diethyl ether, acetylacetone, acetone, dichloromethane, and chloroform.

[0022] Preferably, in step S3, the heating is carried out in an atmospheric, nitrogen, or oxygen environment.

[0023] A third aspect of the present invention provides the application of the aforementioned binuclear alkali metal complex in catalytic alkyne cycloaddition / asymmetric 1,2-rearrangement reactions, wherein the binuclear alkali metal complex has the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is a chiral phosphate anion. The application includes the following steps:

[0024] a. Dissolve substrate A and the binuclear alkali metal complex in an organic solvent to obtain a premix;

[0025] b. Add substrate B to the premix to obtain a mixed solution;

[0026] c. Heat the mixed solution to 55-65℃ and stir for 24-72 hours, then separate to obtain the product;

[0027] Wherein, substrate A is any one of the following structural formulas 1A to 9A:

[0028]

[0029] Substrate B is any one of the following structural formulas 1B to 7B:

[0030]

[0031] In the above general formula, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 They are selected from any one of substituted aryl, substituted heteroaryl, substituted aliphatic group, and substituted heteroaliphatic group.

[0032] Preferably, the molar ratio of substrate A, substrate B, and binuclear alkali metal complex is 1:2-5:0.05-2.

[0033] Preferably, the organic solvent is at least one selected from tetrahydrofuran, toluene, diethyl ether, dichloromethane, 1,2-dichloroethane, and trichloromethane.

[0034] The technical solution of the present invention has the following advantages compared with the prior art:

[0035] The present invention provides a binuclear alkali metal complex with the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is an organophosphate anion or a chiral phosphate anion. The binuclear alkali metal complex is a novel structurally stable polydentate alkali metal phosphate complex, which can be used as a catalytic system for alkyne cycloaddition / asymmetric 1,2-migration rearrangement reactions, solving the problem that traditional transition metal catalytic systems are toxic and cannot enter new catalytic cycles. Attached Figure Description

[0036] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings, wherein...

[0037] Figure 1 This is a schematic diagram of the structure of the binuclear alkali metal complex in Example 11 of the present invention;

[0038] Figure 2 This is a schematic diagram of the structure of the asymmetric 1,2-rearrangement product 1C in Embodiment 11 of the present invention. Detailed Implementation

[0039] Example 1

[0040] This embodiment provides a binuclear alkali metal complex with the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is an organophosphate anion. In this embodiment, M is Na, and L has the following structural formula I:

[0041] In formula I, R 1 R 2 The group is an aliphatic group or a substituted aryl group, such as methyl, ethyl, propyl, olefin, allene, biphenyl, or naphthalene. The general structural formula of the binuclear alkali metal complex provided in this embodiment is:

[0042] Where x, y, and z are selected from positive integers between 0 and 7. In this embodiment, x is 2, y is 3, and z is 3.

[0043] This embodiment also provides a method for preparing the above-mentioned binuclear alkali metal complex, the method comprising the following steps:

[0044] S1. Dissolve the organophosphate ligand LH in chloroform to obtain a phosphate ligand solution;

[0045] S2. Add the alkali metal salt NaHCO3 to the above phosphate ligand solution, with the molar ratio of organic phosphate ligand to alkali metal salt being 1:2, to obtain a mixed reaction solution.

[0046] S3. Heat the mixed reaction solution to 60°C and stir the reaction under atmospheric conditions for 1-2 hours. Filter the product to remove the solvent and dry it to obtain binuclear alkali metal complex crystals.

[0047] Example 2

[0048] This embodiment provides a binuclear alkali metal complex with the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is an organophosphate anion. In this embodiment, M is Li, and L has the following structural formula I:

[0049] In formula I, R 1 R 2 Substituents such as methyl, ethyl, propyl, olefin, allene, biphenyl, or naphthalene can be used. The general structural formula of the binuclear alkali metal complex provided in this embodiment is:

[0050] Where x, y, and z are selected from positive integers between 0 and 7. In this embodiment, x is 1, y is 2, and z is 4.

[0051] This embodiment also provides a method for preparing the above-mentioned binuclear alkali metal complex, the method comprising the following steps:

[0052] S1. Dissolve the organophosphate ligand LH in chloroform to obtain a phosphate ligand solution;

[0053] S2. Add the alkali metal salt Li2CO3 to the above phosphate ligand solution, with the molar ratio of organic phosphate ligand to alkali metal salt being 1:3, to obtain a mixed reaction solution.

[0054] S3. Heat the mixed reaction solution to 60°C and stir the reaction under atmospheric conditions for 1-2 hours. Filter the product to remove the solvent and dry it to obtain binuclear alkali metal complex crystals.

[0055] Example 3

[0056] This embodiment provides a binuclear alkali metal complex with the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is an organophosphate anion. In this embodiment, M is K, and L has the following structural formula I:

[0057] In formula I, R 1 R 2The compounds can be selected from methyl, ethyl, propyl, olefin, allene, biphenyl, or naphthalene, etc. The general structural formula of the binuclear alkali metal complex provided in this embodiment is:

[0058] Where x, y, and z are selected from positive integers between 0 and 7. In this embodiment, x is 5, y is 7, and z is 2.

[0059] This embodiment also provides a method for preparing the above-mentioned binuclear alkali metal complex, the method comprising the following steps:

[0060] S1. Dissolve the organic phosphate ligand LH in chloroform to obtain a phosphate ligand solution;

[0061] S2. Add the alkali metal salt KHCO3 to the above phosphate ligand solution, with the molar ratio of organic phosphate ligand to alkali metal salt being 1:5, to obtain a mixed reaction solution.

[0062] S3. Heat the mixed reaction solution to 60°C and stir the reaction under atmospheric conditions for 1-2 hours. Filter the product to remove the solvent and dry it to obtain binuclear alkali metal complex crystals.

[0063] Example 4

[0064] This embodiment provides a binuclear alkali metal complex with the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is a chiral phosphate anion. In this embodiment, M is Na, and the general structural formula of L is as follows:

[0065] * represents the chiral center, and L is a chiral phosphate anion with configuration (R) or (S). In this embodiment, L is preferably of the following general formula III:

[0066] In structural formula III, R 1 R 2 For H, R 3 R 4 It is a halogenated or substituted aliphatic or aromatic group, such as phenyl, toluene, pentafluorobenzene, naphthalene ring, phenanthrene ring, etc.

[0067] The general structural formula of the binuclear alkali metal complex provided in this embodiment is:

[0068] Where x, y, and z are selected from positive integers between 0 and 7. In this embodiment, x is 1, y is 2, and z is 5.

[0069] This embodiment also provides a method for preparing the above-mentioned binuclear alkali metal complex, the method comprising the following steps:

[0070] S1. Dissolve the chiral phosphate ligand LH in chloroform to obtain a phosphate ligand solution;

[0071] S2. Add the alkali metal salt NaHCO3 to the above phosphate ligand solution, with the molar ratio of chiral phosphate ligand to alkali metal salt being 1:2, to obtain a mixed reaction solution.

[0072] S3. Heat the mixed reaction solution to 60°C and stir the reaction in an oxygen environment for 1-2 hours. Filter the product to remove the solvent and dry it to obtain binuclear alkali metal complex crystals.

[0073] Example 5

[0074] This embodiment provides a binuclear alkali metal complex with the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is a chiral phosphate anion. In this embodiment, M is Rb, and the general structural formula of L is as follows:

[0075] * represents the chiral center, and L is a chiral phosphate anion with configuration (R) or (S). In this embodiment, L is preferably of the following general structural formula IV:

[0076] In structural IV, R 3 R 4 It can be a substituted aryl group, such as phenyl, toluene, pentafluorobenzene, naphthalene ring, phenanthrene ring, etc., or R 3 R 4 It is selected from F, Cl, Br, I, or from alkyl groups such as methyl, ethyl, and propyl.

[0077] The general structural formula of the binuclear alkali metal complex provided in this embodiment is:

[0078] Where x, y, and z are selected from positive integers between 0 and 7. In this embodiment, x is 3, y is 2, and z is 6.

[0079] This embodiment also provides a method for preparing the above-mentioned binuclear alkali metal complex, the method comprising the following steps:

[0080] S1. Dissolve the chiral phosphate ligand LH in chloroform to obtain a phosphate ligand solution;

[0081] S2. Add the alkali metal salt Rb2CO3 to the above phosphate ligand solution, with the molar ratio of chiral phosphate ligand to alkali metal salt being 1:3, to obtain a mixed reaction solution.

[0082] S3. Heat the mixed reaction solution to 60°C and stir the reaction in an oxygen environment for 1-2 hours. Filter the product to remove the solvent and dry it to obtain binuclear alkali metal complex crystals.

[0083] Example 6

[0084] This embodiment provides a binuclear alkali metal complex with the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is a chiral phosphate anion. In this embodiment, M is Cs, and the general structural formula of L is as follows:

[0085] * represents the chiral center, and L is a chiral phosphate anion with configuration (R) or (S). In this embodiment, L is preferably of the following general structural formula VIII:

[0086] In structural form VIII, R 1 R 2 R 3 For H, R 4 R 5 Substituted aliphatic or aromatic groups, such as phenyl, toluene, pentafluorobenzene, naphthalene ring, phenanthrene ring, methyl, ethyl, propyl, etc.

[0087] The general structural formula of the binuclear alkali metal complex provided in this embodiment is:

[0088] Where x, y, and z are selected from positive integers between 0 and 7. In this embodiment, x is 4, y is 5, and z is 7.

[0089] This embodiment also provides a method for preparing the above-mentioned binuclear alkali metal complex, the method comprising the following steps:

[0090] S1. Dissolve the chiral phosphate ligand LH in chloroform to obtain a phosphate ligand solution;

[0091] S2. Add the alkali metal salt Cs2CO3 to the above phosphate ligand solution, with the molar ratio of chiral phosphate ligand to alkali metal salt being 1:4.5, to obtain a mixed reaction solution.

[0092] S3. Heat the mixed reaction solution to 60°C and stir the reaction under nitrogen atmosphere for 1-2 hours. Filter the product to remove the solvent and dry it to obtain binuclear alkali metal complex crystals.

[0093] Example 7

[0094] This embodiment provides a binuclear alkali metal complex with the general formula M2L2·nH2O, where M is any one of the alkali metals Li, Na, K, Rb, and Cs, and L is a chiral phosphate anion. In this embodiment, M is Cs, and the general structural formula of L is as follows:

[0095] * represents the chiral center, and L is a chiral phosphate anion with configuration (R) or (S). In this embodiment, L is preferably of the following general structural formula IX:

[0096] In structural form IX, R 1 For H, R 2 For H, R 4 Substituted aliphatic or aromatic groups, such as methyl, ethyl, propyl, phenyl, toluene, pentafluorobenzene, naphthalene ring, phenanthrene ring, etc., or R 4 It is one of F, Cl, Br, and I, Y is an oxygen atom, and n is 2.

[0097] The general structural formula of the binuclear alkali metal complex provided in this embodiment is:

[0098] Where x, y, and z are selected from positive integers between 0 and 7. In this embodiment, x is 4, y is 5, and z is 7.

[0099] This embodiment also provides a method for preparing the above-mentioned binuclear alkali metal complex, the method comprising the following steps:

[0100] S1. Dissolve the chiral phosphate ligand LH in chloroform to obtain a phosphate ligand solution;

[0101] S2. Add the alkali metal salt Cs2CO3 to the above phosphate ligand solution, with the molar ratio of chiral phosphate ligand to alkali metal salt being 1:4.5, to obtain a mixed reaction solution.

[0102] S3. Heat the mixed reaction solution to 60°C and stir the reaction under nitrogen atmosphere for 1-2 hours. Filter the product to remove the solvent and dry it to obtain binuclear alkali metal complex crystals.

[0103] Example 8

[0104] This embodiment provides an application of the binuclear alkali metal complex provided in this application in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reactions, particularly the application of the resulting binuclear alkali metal chiral complex in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reactions when L-chiral phosphate anions are present. Specifically, this application includes:

[0105] a. Dissolve substrate A and the binuclear alkali metal complex provided in Example 4 in toluene to obtain a premix;

[0106] b. Add substrate B to the premix to obtain a mixed solution, wherein the molar ratio of substrate A, substrate B, and binuclear alkali metal complex is 1:2:0.05.

[0107] c. Heat the mixed solution to 60°C and stir for 72 hours to separate the product.

[0108] In this embodiment, substrate A can adopt any one of the following structural formulas 1A to 9A:

[0109]

[0110] Substrate B is any one of the following structural formulas 1B to 7B:

[0111]

[0112] In general formulas 1A to 7A and 1B to 7B, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 They are selected from any one of substituted aryl, substituted heteroaryl, substituted aliphatic group, and substituted heteroaliphatic group.

[0113] In this embodiment, the general formula for substrate A is 1A, where R 1 R 2 For substituted aryl groups, such as benzene containing substituents, pyridine, isoquinoline, quinoline, etc., R 4 R is an alkyl group such as methyl, ethyl, propyl, or phenyl, substituted phenyl, etc. 4 It can also be a halogen, and the general formula for substrate B is 1B, where R 6 R 7 It is a substituted aromatic group or alkyl group, such as methyl, ethyl, propyl, cycloaryl, phenyl, substituted phenyl, etc.

[0114] Alkynes are versatile synthons widely used in addition, cyclization, and other cascade reactions. Alkyne cyclization / 1,2-migration cascade reactions have shown significant advantages in the synthesis of complex natural products. However, due to the strict stereochemical retention of α-tertiary alcohols during migration rearrangement, dynamic kinetic transformation cannot be achieved. This embodiment utilizes the aforementioned carbonyl base to achieve an asymmetric 1,2-migration rearrangement process through its cycloaddition reaction with alkynes. This strategy faces several challenges, the most significant being finding a suitable catalytic system. This is because such carbonyl bases have a classic bidentate ligand structure, and many transition metals can form stable complexes with them, causing catalyst poisoning and preventing entry into new catalytic cycles. The binuclear alkali metal complex provided in this application solves this technical problem due to the presence of a weakly coordinating alkali metal.

[0115] Example 9

[0116] This embodiment provides an application of the binuclear alkali metal complex provided in this application in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reactions, particularly the application of the resulting binuclear alkali metal chiral complex in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reactions when L-chiral phosphate anions are present. Specifically, this application includes:

[0117] a. Dissolve substrate A and the binuclear alkali metal complex provided in Example 5 in toluene to obtain a premix;

[0118] b. Add substrate B to the premix to obtain a mixed solution, wherein the molar ratio of substrate A, substrate B, and binuclear alkali metal complex is 1:3:0.1.

[0119] c. Heat the mixed solution to 60°C and stir for 72 hours to separate the product.

[0120] In this embodiment, substrate A is structural formula 2A from embodiment 8, and substrate B is 1B from embodiment 8, wherein R 6 R 7 Substituted alkyl, phenyl, or heterocyclic aryl groups can be used, such as methyl, ethyl, propyl, phenyl, substituted phenyl, etc.

[0121] Example 10

[0122] This embodiment provides an application of the binuclear alkali metal complex provided in this application in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reactions, particularly the application of the resulting binuclear alkali metal chiral complex in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reactions when L-chiral phosphate anions are present. Specifically, this application includes:

[0123] a. Dissolve substrate A and the binuclear alkali metal complex provided in Example 6 in toluene to obtain a premix;

[0124] b. Add substrate B to the premix to obtain a mixed solution, wherein the molar ratio of substrate A, substrate B, and binuclear alkali metal complex is 1:5:0.2.

[0125] c. Heat the mixed solution to 60°C and stir for 72 hours to separate the product.

[0126] In this embodiment, substrate A is structural formula 3A from embodiment 8, and substrate B is 4B from embodiment 8, wherein R 1 For the substituted aryl group, R 4 For aryl, R 6 For the substituted aryl group.

[0127] Example 11

[0128] This embodiment provides a binuclear alkali metal complex, which is prepared by the following steps:

[0129] S1. At room temperature, weigh 0.1 g of chiral phosphate ligand (2s,11bS)-4-hydroxy-2,6-bis(perfluorophenyl)dinaphtho[2,1-d:1',2'-f][1,3,2]diox aphosphepine 4-oxide and place it in a 50 ml round-bottom flask. Add 20 ml of chloroform to obtain the phosphate ligand solution.

[0130] S2. Add 0.03g of sodium bicarbonate to the phosphate ligand solution to obtain a mixed reaction solution.

[0131] S3. Heat the mixed reaction solution to 60℃ and keep stirring for 1-2 hours. Filter and let the filtrate stand for a period of time to obtain transparent crystals. After drying the transparent crystals, the binuclear alkali metal complex Na2P2·7H2O is obtained.

[0132] The structure of the binuclear alkali metal complex provided in this embodiment is as follows: Figure 1 As shown, each building unit (SBU) contains two Na + Seven coordinated H₂O molecules and two completely deprotonated ligands form an electroneutrally neutral unit. Na₁ is connected to O₃ and O₇ ligands, and Na₂ is connected to O₃ ligands. Na₁ and Na₂ are bridged by two water molecules (O₉ and O₁₀). The distance between Na₁ and Na₂ is... It is worth noting that the fluorine atom F20 near Na1 is connected by a relatively weak coordinate bond, and the distance between Na1 and F20 is... The formation of Na-F bonds increases the stability of the entire crystal.

[0133] The binuclear alkali metal complex provided in this embodiment can be applied to catalyze alkyne cycloaddition / 1,2-asymmetric rearrangement reactions, specifically including:

[0134] a. At room temperature, the substrate isoquinolin-1-yl(phenyl)methanone (23.3 mg, 0.1 mmol) and the catalyst Na2P2·7H2O (7.7 mg, 0.005 mmol) were dissolved in 2 ml of toluene to obtain a premix.

[0135] b. Add the substrate ((trifluoromethyl)sulfonyl)ethynyl)benzene (46.8 mg, 0.2 mmol) to the premix to obtain a mixed solution.

[0136] c. Heat the mixed solution to 60°C and stir for 72 hours. Separate the obtained reactants by column chromatography to obtain the asymmetric 1,2-rearrangement product 1C.

[0137] The structural formula of rearrangement product 1C is:

[0138] Its structural diagram is shown in Figure 2.

[0139] Experimental Example

[0140] 1. X-ray crystallographic data of the binuclear alkali metal complex provided in Example 11 were tested. The test results can be obtained from http: / / www.ccdc.cam.ac.uk / data_request / cif (Cambridge Crystallographic Data Centre), crystal accession number CCDC214407.

[0141] The test data is shown in Table 1:

[0142] Table 1

[0143]

[0144]

[0145] 2. Crystal data of the asymmetric 1,2-rearrangement product 1C obtained in Example 10 were tested. The test results are shown in Table 2.

[0146] Table 2

[0147]

[0148] The other test results for 1C are as follows:

[0149] 1 H NMR (400MHz, CDCl3): δ8.44(d,J=7.7Hz,1H),7.63(s,3H),7.54(s,1H),7.46(td,J=7.6,1.5Hz, 1H),7.40(m,2H),7.31(m,3H),7.23-7.16(m,3H),6.36(d,J=7.4Hz,1H),6.20(d,J=7.4Hz,1H).

[0150] 13C NMR (101MHz, CDCl3): δ188.85,175.75,135.66,131.95,130.42,129.75,129.11,128.99,128.91,128.71, 128.46,127.69,127.48,125.32,125.08,124.81,121.58,120.65,119.62,118.34,115.10,100.02,73.45.

[0151] 19 F NMR (376MHz, CDCl3): δ-79.52;

[0152] IR:1713,1515,1461,1429,1365,1309,1211,1121,778cm -1 .

[0153] All the above test data indicate that a crystalline product with good crystallinity was obtained.

[0154] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A binuclear alkali metal complex, characterized in that, The binuclear alkali metal complex is prepared by the following steps: S1. At room temperature, weigh the chiral phosphate ligand (2s,11bS)-4-hydroxy-2,6-bis(perfluorophenyl)dinaphtho[2,1-d:1',2'-f][1,3,2]dioxopyrazine-oct-4-one and place it in a round-bottom flask. Add chloroform to obtain the phosphate ligand solution. S2. Add sodium bicarbonate to the phosphate ligand solution to obtain a mixed reaction solution; S3. Heat the mixed reaction solution to 60°C and keep stirring for 1-2 hours. Filter the solution and let the filtrate stand for a period of time to obtain transparent crystals. After drying the transparent crystals, the binuclear alkali metal complex is obtained. The structure of the binuclear alkali metal complex is shown in Figure 1.

2. The application of the binuclear alkali metal complex as described in claim 1 in the catalytic cycloaddition / asymmetric 1,2-rearrangement reaction of alkynes, the application comprising the following steps: a. At room temperature, 0.1 mmol of the substrate 1-isoquinolinylbenzophenone and 0.005 mmol of the catalyst binuclear alkali metal complex were dissolved in 2 ml of toluene to obtain a premix. b. Add 0.2 mmol of the substrate trifluoromethylsulfonylethynylbenzene to the premix to obtain a mixture; c. The mixture is heated to 60°C and stirred for 72 hours. The resulting reactants are separated by column chromatography to obtain the asymmetric 1,2-rearrangement product 1C. 。

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