Binuclear alkali metal complex as well as preparation method and application thereof

Abstract

The invention discloses a binuclear alkali metal complex and a preparation method and application thereof, the general formula of the binuclear alkali metal complex is M2L2.nH2O, M is any one of alkali metals Li, Na, K, Rb and Cs, L is an organic phosphate anion or a chiral phosphate anion, and the binuclear alkali metal complex is a novel alkali metal phosphate polydentate complex with a stable structure. The catalyst can serve as a catalytic system to be applied to alkyne cycloaddition / asymmetric 1, 2-migration rearrangement reaction, and the problem that a traditional transition metal catalytic system cannot enter a new catalytic cycle due to catalyst poisoning is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of metal complexes, and in particular relates to a binuclear alkali metal complex and a preparation method and application thereof. Background Art

[0002] The process in which molecules or ions combine with metal ions to form very stable new ions is called complex reaction, also known as coordination reaction. The compound composed of complex ions or complex molecules is called a complex. In the complex, the central ion is the core part, which is located in the center of the complex ion and is generally a positively charged ion (mostly metal ions). The ions or molecules complexed with the central ion are ligands.

[0003] Transition metals have more empty orbitals and suitable atomic radii, and are easy to accept electrons provided by ligands to form stable complexes, playing an important role in the technical path of asymmetric catalysis. Over the past half century, the transition metal chiral ligand catalytic mode has led to the vigorous development of asymmetric organic catalysis, which is widely used in organic synthesis reactions such as asymmetric hydrogenation reactions, coupling reactions, and carbon hydrogenation activation. However, transition metals have problems such as scarce reserves, high prices, and large side effects on the human body. Especially in the pharmaceutical industry and other fields, the residues of heavy metals need to be strictly controlled. These problems limit the application of transition metals in this field. In order to solve the above problems, in recent years, the industry has gradually developed solutions for preparing complexes using alkali metals. Alkali metals have the advantages of abundant reserves, low prices and good biocompatibility. From the perspective of green chemistry and sustainable development, alkali metals are considered to be the most ideal substitutes for transition metals in the field of asymmetric catalysis.

[0004] In an ideal asymmetric catalytic process, the metal and the substrate reversibly bind or leave through weak interactions, forming an asymmetric catalytic cycle. For substrates with strong complexing ability, strong interactions with transition metals with strong Lewis acidity are likely to occur, resulting in catalyst deactivation and the inability to continue the catalytic cycle. However, alkali metals with weak Lewis acidity may be transformed into an advantage in catalyzing the reaction of strongly coordinated substrates. Due to their special atomic structure, alkali metals most commonly exist as monovalent metal cations after the outermost electrons are removed. They have the characteristics of low electronegativity, small charge number, and large radius. They are typical Lewis weak acids and are difficult to form stable complexes with Lewis base ligands. At the same time, alkali metal ions cannot provide more empty orbitals for organic ligands, and it is difficult to form multi-dentate stable complexes with chiral ligands. At present, except for a few organic compounds such as crown ethers and phenols that can form stable complexes with alkali metals, other forms of alkali metal chiral complexes have rarely been reported. In recent years, organophosphate compounds have gradually attracted widespread attention as metal ligands. Due to its special phosphoric acid functional group, it has unique coordination ability: first, the carboxylic acid anion formed after the deprotonation of organic phosphoric acid has a strong electron-donating ability, which enables it to form a relatively stable coordination bond with the metal. Secondly, due to the variability of the degree of deprotonation of carboxylic acid, it has a variety of coordination forms, but there is no report on alkali metal organic phosphoric acid complexes.

[0005] In view of this, researching and developing a new type of alkali metal organophosphate complex and applying it to the field of asymmetric catalysis has become a technical problem that needs to be solved urgently. 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, thereby proposing a binuclear alkali metal complex and a preparation method and application thereof.

[0007] In order to solve the above technical problems, the technical solution of the present invention is:

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

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

[0010]

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

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

[0013]

[0014]

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

[0016] The second aspect of the present invention provides a method for preparing the binuclear alkali metal complex, which comprises the following steps:

[0017] S1, dissolving a 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, adding an alkali metal salt MnXn to the phosphate ligand solution, wherein the molar ratio of the phosphate ligand to the 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, heating the mixed reaction solution and stirring the mixture for reaction, filtering and drying the product to obtain the binuclear alkali metal complex.

[0020] Preferably, X is a halogen ion, a cyanide ion, an azide ion, a bicarbonate, a carbonate, a nitrate, a sulfate, a sulfonate, an oxalate, an acetate, a perchlorate, a trifluoroacetate, a trichloroacetate, a trifluoromethanesulfonate, a tetrafluoroborate, a p-toluate, a p-toluenesulfonate, an o-nitrophenoloxy, a p-nitrophenoloxy, a m-nitrophenoloxy, a 2,4-dinitrophenoloxy, a 3-5-dinitrophenoloxy, a 2,4,6-trinitrophenoloxy, a 3,5-dichlorophenoloxy, a 3,5-difluorophenoloxy, a 3,5-di-trifluoromethylphenoloxy or a pentafluorophenoloxy anion.

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

[0022] Preferably, in step S3, the heating is performed in an atmosphere of air, nitrogen or oxygen.

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

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

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

[0026] c. heating the mixed solution to 55-65° C. and stirring for 24-72 hours to separate and 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 Each of them is selected from a substituted aryl group, a substituted heteroaryl group, a substituted aliphatic group, and a substituted heteroaliphatic group.

[0032] Preferably, the molar ratio of the 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 of tetrahydrofuran, toluene, diethyl ether, dichloromethane, 1,2-dichloroethane and chloroform.

[0034] The above 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, the general formula of which is M2L2·nH2O, wherein M is any one of alkali metals Li, Na, K, Rb, and Cs, and L is an organic phosphate anion or a chiral phosphate anion. The binuclear alkali metal complex is a novel structurally stable alkali metal phosphate multidentate complex, which can be used as a catalytic system for alkyne cycloaddition / asymmetric 1,2-migration rearrangement reaction, thereby solving the problem that a traditional transition metal catalytic system is toxic and cannot enter a new catalytic cycle. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein

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

[0038] Figure 2 It is a schematic diagram of the structure of the asymmetric 1,2-rearrangement product 1C in Example 11 of the present invention. DETAILED DESCRIPTION

[0039] Example 1

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

[0041] In Formula I, R 1 , R 2 is an aliphatic group or a substituted aromatic 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] Wherein, x, y, and z are respectively 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 binuclear alkali metal complex, which comprises the following steps:

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

[0045] S2, adding alkali metal salt NaHCO3 to the above-mentioned phosphate ligand solution, wherein the molar ratio of the organic phosphate ligand to the alkali metal salt is 1:2, to obtain a mixed reaction solution;

[0046] S3. The mixed reaction solution is heated to 60° C. and stirred for reaction for 1-2 hours under atmospheric conditions. The product is filtered to remove the solvent and dried to obtain binuclear alkali metal complex crystals.

[0047] Example 2

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

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

[0050] Wherein, x, y, and z are respectively 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 binuclear alkali metal complex, which comprises the following steps:

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

[0053] S2, adding alkali metal salt Li2CO3 to the above-mentioned phosphate ligand solution, wherein the molar ratio of the organic phosphate ligand to the alkali metal salt is 1:3, to obtain a mixed reaction solution;

[0054] S3. The mixed reaction solution is heated to 60° C. and stirred for reaction for 1-2 hours under atmospheric conditions. The product is filtered to remove the solvent and dried to obtain binuclear alkali metal complex crystals.

[0055] Example 3

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

[0057] In Formula I, R 1 , R 2It 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] Wherein, x, y, and z are respectively 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 binuclear alkali metal complex, which comprises the following steps:

[0060] S1, dissolving the organophosphate ligand LH in chloroform to obtain a phosphate ligand solution;

[0061] S2, adding alkali metal salt KHCO3 to the above-mentioned phosphate ligand solution, wherein the molar ratio of the organic phosphate ligand to the alkali metal salt is 1:5, to obtain a mixed reaction solution;

[0062] S3. The mixed reaction solution is heated to 60° C. and stirred for reaction for 1-2 hours under atmospheric conditions. The product is filtered to remove the solvent and dried to obtain binuclear alkali metal complex crystals.

[0063] Example 4

[0064] This embodiment provides a binuclear alkali metal complex, the general formula of which is M2L2·nH2O, where M is any one of 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 the following structural formula II:

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

[0066] In structural formula III, R 1 , R 2 For H, R 3 , R 4 It is a halogen 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] Wherein, x, y, and z are respectively 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 binuclear alkali metal complex, which comprises the following steps:

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

[0071] S2, adding alkali metal salt NaHCO3 to the above-mentioned phosphate ligand solution, wherein the molar ratio of the chiral phosphate ligand to the alkali metal salt is 1:2, to obtain a mixed reaction solution;

[0072] S3. Heat the mixed reaction solution to 60° C. and stir the reaction under 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, the general formula of which is M2L2·nH2O, where M is any one of alkali metals Li, Na, K, Rb, and Cs, and L is a chiral phosphate anion. In this embodiment, M is Rb, and the general formula of L is the following structural formula II:

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

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

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

[0078] Wherein, x, y, and z are respectively 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 binuclear alkali metal complex, which comprises the following steps:

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

[0081] S2, adding alkali metal salt Rb2CO3 to the above-mentioned phosphate ligand solution, wherein the molar ratio of the chiral phosphate ligand to the alkali metal salt is 1:3, to obtain a mixed reaction solution;

[0082] S3. Heat the mixed reaction solution to 60° C. and stir the reaction under 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, the general formula of which is M2L2·nH2O, where M is any one of alkali metals Li, Na, K, Rb, and Cs, and L is a chiral phosphate anion. In this embodiment, M is Cs, and the general formula of L is the following structural formula II:

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

[0086] In structural formula VIII, R 1 , R 2 , R 3 For H, R 4 , R 5 It is a substituted aliphatic group or aromatic group, 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] Wherein, x, y, and z are respectively 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 binuclear alkali metal complex, which comprises the following steps:

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

[0091] S2, adding alkali metal salt Cs2CO3 to the above-mentioned phosphate ligand solution, wherein the molar ratio of the chiral phosphate ligand to the alkali metal salt is 1:4.5, to obtain a mixed reaction solution;

[0092] S3. Heat the mixed reaction solution to 60° C. and stir the reaction under a nitrogen environment 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, the general formula of which is M2L2·nH2O, where M is any one of alkali metals Li, Na, K, Rb, and Cs, and L is a chiral phosphate anion. In this embodiment, M is Cs, and the general formula of L is the following structural formula II:

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

[0096] In the structural formula IX, R 1 For H, R 2 For H, R 4 is a substituted aliphatic or aromatic group, such as methyl, ethyl, propyl, phenyl, toluene, pentafluorobenzene, naphthalene ring, phenanthrene ring, etc., or R 4 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] Wherein, x, y, and z are respectively 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 binuclear alkali metal complex, which comprises the following steps:

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

[0101] S2, adding alkali metal salt Cs2CO3 to the above-mentioned phosphate ligand solution, wherein the molar ratio of the chiral phosphate ligand to the alkali metal salt is 1:4.5, to obtain a mixed reaction solution;

[0102] S3. Heat the mixed reaction solution to 60° C. and stir the reaction under a nitrogen environment 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 the present application in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reaction, especially when the L-chiral phosphate anion is used, the application of the obtained binuclear alkali metal chiral complex in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reaction, specifically, the application includes:

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

[0106] b. Adding 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. The mixed solution was heated to 60° C. and stirred for 72 h 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 the general formulae 1A to 7A and 1B to 7B, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Each of them is selected from a substituted aryl group, a substituted heteroaryl group, a substituted aliphatic group, and a substituted heteroaliphatic group.

[0113] In this embodiment, the general formula of substrate A is 1A, wherein R 1 , R 2 is a substituted aryl group, such as substituted benzene, pyridine, isoquinoline, quinoline, etc., R 4 is an alkyl group such as methyl, ethyl, propyl or phenyl, substituted phenyl, etc., R 4 It can also be a halogen. The general formula of substrate B is 1B, wherein 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 a versatile synthon widely used in addition, cyclization and other cascade reactions. Alkyne cyclization / 1,2-migration cascade reactions have shown great advantages in the synthesis of complex natural products, but since α-tertiary alcohols show strict stereochemical retention during the migration rearrangement process, dynamic kinetic transformation cannot be achieved. In this embodiment, by adopting the above-mentioned carbonyl substrate, an asymmetric 1,2-migration rearrangement process can be achieved by utilizing its cycloaddition reaction with alkynes. This strategy faces many challenges, the biggest of which is how to find a suitable catalytic system, because this type of carbonyl substrate is a classic bidentate ligand structure, and many transition metals can form stable complexes with it, causing poisoning of the catalyst and being unable to enter a new catalytic cycle. The binuclear alkali metal complex provided in the present application solves this technical problem because it has an alkali metal with weak coordination ability.

[0115] Example 9

[0116] This embodiment provides an application of the binuclear alkali metal complex provided in the present application in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reaction, especially when the L-chiral phosphate anion is used, the application of the obtained binuclear alkali metal chiral complex in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reaction, specifically, the application includes:

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

[0118] b. Adding 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. The mixed solution was heated to 60° C. and stirred for 72 h to separate the product.

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

[0121] Example 10

[0122] This embodiment provides an application of the binuclear alkali metal complex provided in the present application in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reaction, especially when the L-chiral phosphate anion is used, the application of the obtained binuclear alkali metal chiral complex in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reaction, specifically, the application includes:

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

[0124] b. Adding 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. The mixed solution was heated to 60° C. and stirred for 72 h to separate the product.

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

[0127] Embodiment 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 a phosphate ligand solution.

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

[0131] S3. The mixed reaction solution is heated to 60°C and stirred for 1-2 hours, filtered, and the filtrate is allowed to stand for a period of time to obtain transparent crystals. The transparent crystals are dried to obtain a binuclear alkali metal complex: Na2P2·7H2O.

[0132] The structure of the binuclear alkali metal complex provided in this embodiment is as follows Figure 1 As shown, each building block (SBU) contains two Na + , seven coordinated H2O and two completely deprotonated ligands to form an electrically neutral unit. Na1 is connected to O3 and O7 on the ligand, and Na2 is connected to O3 on the ligand. Na1 and Na2 are connected in a bridging manner through two waters (O9, O10). The distance between Na1…Na2 is It is worth noting that the fluorine atom F20 near Na1 is connected by a weak coordination bond, and the distance between Na1…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 used to catalyze alkyne cycloaddition / 1,2-asymmetric rearrangement reactions, specifically including:

[0134] a. At room temperature, dissolve the substrate isoquinolin-1-yl(phenyl)methanone (23.3 mg, 0.1 mmol) and the catalyst Na2P2·7H2O (7.7 mg, 0.005 mmol) 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. The mixed solution was heated to 60° C. and stirred for 72 h. The obtained reactants were separated by column chromatography to obtain the asymmetric 1,2-rearrangement product 1C.

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

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

[0139] Experimental example

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

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

[0142] Table 1

[0143]

[0144]

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

[0146] Table 2

[0147]

[0148] The test results of other data of 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] The above test data all show that a crystalline product with good crystallinity is obtained.

[0154] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A binuclear alkali metal complex, characterized in that The general formula of the binuclear alkali metal complex is M2L2·nH2O, where M is any one of alkali metals Li, Na, K, Rb, and Cs, and L is an organic phosphate anion or a chiral phosphate anion. When L is an organic phosphate anion, the general formula of L is Alternatively, when L is a chiral organic phosphate anion, the general formula of L is In Formula I, R 1 , R 2 is selected from substituted aliphatic groups, substituted heteroaliphatic groups, substituted aryl groups, and substituted heteroaryl groups; in Formula II, * is a chiral center.

2. The binuclear alkali metal complex according to claim 1, characterized in that The general structural formula of the binuclear alkali metal complex is: n=x+y+z, x, y, z are respectively selected from positive integers between 0 and 7.

3. The binuclear alkali metal complex according to claim 1 or 2, characterized in that When L is a chiral organic phosphate anion, L is any one of the following structural formulas III to IX: In the above general formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are selected from any one of hydrogen, halogen, substituted aliphatic group, substituted heteroaliphatic group, substituted aryl group, substituted heteroaryl group; Y is any one of N, O, S atom; n is a positive integer between 0-7.

4. A method for preparing the binuclear alkali metal complex according to any one of claims 1 to 3, characterized in that: The steps include: S1, dissolving a 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; S2, adding an alkali metal salt MnXn to the phosphate ligand solution, wherein the molar ratio of the phosphate ligand to the 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; S3, heating the mixed reaction solution to 55-65° C. and stirring the reaction, filtering and drying the product to obtain the binuclear alkali metal complex.

5. The preparation method according to claim 4, characterized in that: X is any one of a halogen ion, a cyanide ion, an azide ion, a bicarbonate, a carbonate, a nitrate, a sulfate, a sulfonate, an oxalate, an acetate, a perchlorate, a trifluoroacetate, a trichloroacetate, a trifluoromethanesulfonate, a tetrafluoroborate, a p-toluate, a p-toluenesulfonate, an o-nitrophenoloxy, a p-nitrophenoloxy, a m-nitrophenoloxy, a 2,4-dinitrophenoloxy, a 3-5-dinitrophenoloxy, a 2,4,6-trinitrophenoloxy, a 3,5-dichlorophenoloxy, a 3,5-difluorophenoloxy, a 3,5-di-trifluoromethylphenoloxy or a pentafluorophenoloxy anion.

6. The preparation method according to claim 5, characterized in that: The organic solvent is at least one of N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, toluene, methanol, ethanol, acetonitrile, ether, acetylacetone, acetone, dichloromethane and chloroform.

7. The preparation method according to claim 6, characterized in that: In the step S3, the heating is performed in an atmosphere of air, nitrogen or oxygen.

8. Use of the binuclear alkali metal complex according to any one of claims 1 to 3 in catalyzing alkyne cycloaddition / asymmetric 1,2-rearrangement reaction, wherein the binuclear alkali metal complex has the general formula of M2L2·nH2O, M is any one of alkali metals Li, Na, K, Rb, Cs, and L is a chiral phosphate anion, and the use comprises the following steps: a. dissolving substrate A and the binuclear alkali metal complex in an organic solvent to obtain a premix; b. adding substrate B to the premix to obtain a mixed solution; c. heating the mixed solution to 55-65° C. and stirring for 24-72 hours to separate and obtain the product; Wherein substrate A is any one of the following structural formulas 1A to 9A: Substrate B is any one of the following structural formulas 1B to 7B: In the above general formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Each of them is selected from a substituted aryl group, a substituted heteroaryl group, a substituted aliphatic group, and a substituted heteroaliphatic group.

9. The use according to claim 8, characterized in that: The molar ratio of the substrate A, substrate B and binuclear alkali metal complex is 1:2-5:0.05-2.

10. The use according to claim 9, characterized in that: The organic solvent is at least one of tetrahydrofuran, toluene, ether, dichloromethane, 1,2-dichloroethane and chloroform.

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