A binuclear gold catalyst and its preparation method and application

Abstract

The present invention belongs to the field of catalyst technology, and discloses a binuclear gold catalyst and a preparation method and application thereof. The binuclear gold catalyst has a structure shown in Formula I: wherein the X group is selected from any one of bis(trifluoromethanesulfonyl)imide, trifluoromethanesulfonate, tetrafluoroborate, hexafluoroantimonate, trifluoroacetate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, acetate, and benzoate; and is a bisphosphine ligand. The binuclear gold catalyst invented by the present invention can be used to catalyze the nitrogen-hydrogen insertion reaction of diazo and amine, the cycloaddition reaction of enyne aldehyde, and the cyclization reaction of enyne ketone. In the above-mentioned application, the binuclear gold catalyst exhibits good stability and high tolerance to water, has high catalytic efficiency and novel reaction selectivity, and has a high product yield.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and particularly relates to a binuclear gold catalyst and a preparation method and application thereof. Background Art

[0002] In the past few decades, homogeneous gold (I) catalysts have been rapidly and widely developed due to their special properties. The origin of gold (I) catalysts can be traced back to 1986, when Ito et al. studied the asymmetric aldol condensation reaction catalyzed by chiral gold (I)-phosphine complexes; in 1987, Utimoto's group first realized the homogeneous gold (I) catalyst-catalyzed addition reaction of nucleophiles and alkynes; in 1998, Teles et al. proved that gold (I) complexes can effectively activate alkynes; after 2000, gold (I) catalyst-catalyzed reactions have developed into one of the most active areas in organometallic research.

[0003] Nowadays, gold (I) catalyst catalysis has become an important means of preparing drug skeletons and natural products. Its reaction conditions are mild, selectivity is good, efficiency is high, it has good substrate tolerance and environmental friendliness, and in most cases, gold (I) catalysts are insensitive to air and water. However, due to the high cost and low catalytic efficiency of gold (I) catalysts, these shortcomings have hindered the further development of gold (I) catalysts. Based on the cost of gold and catalytic turnover rate, researchers have been trying to synthesize more efficient gold (I) catalysts.

[0004] Therefore, there is an urgent need to provide a gold (I) catalyst with high catalytic efficiency. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a binuclear gold catalyst and a preparation method and application thereof. The binuclear gold catalyst of the present invention has two active centers, which can synergistically participate in the reaction to activate the substrate, thereby greatly reducing the energy barrier of the reaction, thereby improving the catalytic efficiency. The raw materials used in the preparation method of the binuclear gold catalyst of the present invention are easy to obtain, and the synthesis route is simple. The binuclear gold catalyst can be obtained by mixing and reacting a commercially available bisphosphine ligand, a gold source, and a salt containing an X group. The binuclear gold catalyst can be used to catalyze the nitrogen-hydrogen insertion reaction of diazo and amine, the cycloaddition reaction of enyne aldehyde, and the cyclization reaction of enyne ketone, and has a wide range of uses.

[0006] A first aspect of the present invention provides a binuclear gold catalyst.

[0007] Specifically, a binuclear gold catalyst has a structure shown in Formula I:

[0008]

[0009] Wherein, the X group is selected from any one of bis(trifluoromethanesulfonyl)imide, trifluoromethanesulfonate, tetrafluoroborate, hexafluoroantimonate, trifluoroacetate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, acetate, and benzoate; It is a bisphosphine ligand.

[0010] Preferably, the Select any one of the following structures:

[0011]

[0012] Wherein, the R1 group is a phenyl group or a substituted phenyl group.

[0013] Above It is a bisphosphine ligand (Ph represents phenyl). The above Ⅱ-A, Ⅱ-B, Ⅱ-C, Ⅱ-D, Ⅱ-E, Ⅱ-F, Ⅱ-G, Ⅱ-H, Ⅱ-II, Ⅱ-J, Ⅱ-K, Ⅱ-L, Ⅱ-M, and Ⅱ-N are the numbers of specific bisphosphine ligands.

[0014] Preferably, the R1 group is a phenyl group substituted with a methyl group, a tert-butyl group or a methoxy group at the para position and a methyl group or a tert-butyl group at the ortho position.

[0015] Preferably, the binuclear gold catalyst is selected from any one of the following structures:

[0016]

[0017]

[0018] The above C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, and C14 are numbers assigned to specific binuclear gold catalysts.

[0019] A second aspect of the present invention provides a method for preparing a binuclear gold catalyst.

[0020] Specifically, a method for preparing a binuclear gold catalyst comprises the following steps:

[0021] The diphosphine ligand is added into a solution containing a gold source, and then a salt containing an X group is added to react and precipitate to obtain the binuclear gold catalyst.

[0022] Preferably, after the reaction is completed, the concentrated solution is obtained by distillation under reduced pressure, and the binuclear gold catalyst is obtained by precipitation through a poor solvent.

[0023] Preferably, the reaction temperature is 5 to 100°C, preferably 10 to 100°C.

[0024] Preferably, the reaction time is 0.1 to 48 h, preferably 0.5-40 h, for example 1 h, 5 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h.

[0025] Preferably, the gold source is chloro(dimethyl sulfide)gold and / or chloro(tetrahydrothiophene)gold.

[0026] Preferably, the salt containing the X group is a sodium salt, a lithium salt or a silver salt containing the X group.

[0027] Preferably, the amount of the bisphosphine ligand used is 0.5 to 10 molar equivalents of the gold source, such as 1 to 8 molar equivalents.

[0028] Preferably, the amount of the salt containing the X group is 0.5 to 10 molar equivalents of the gold source, for example 1 to 8 molar equivalents.

[0029] Preferably, the solvent in the solution containing the gold source is selected from at least one of dichloromethane, 1,2-dichloroethane, chloroform, acetone or toluene.

[0030] Preferably, the poor solvent is selected from at least one of n-pentane, cyclopentane or diethyl ether.

[0031] Preferably, shaking, stirring or ultrasonic treatment is performed during the reaction.

[0032] The third aspect of the present invention provides an application of a binuclear gold catalyst.

[0033] Specifically, the binuclear gold catalyst is used to catalyze the nitrogen-hydrogen insertion reaction of diazo and amine, the cycloaddition reaction of enyne aldehyde or the cyclization reaction of enyne ketone.

[0034] Preferably, in the application, the amount of the binuclear gold catalyst is 0.01-10% of the total molar amount of the reactants, for example 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.

[0035] Preferably, the steps of catalyzing the nitrogen-hydrogen insertion reaction of diazo and amine are as follows:

[0036] In a nitrogen atmosphere, a solution of a diazo compound, a solution of an amine compound and a solution of the binuclear gold catalyst are added to a reactor, and stirred to react; after the reaction, the solvent is removed from the reaction solution by vacuum distillation to a constant weight, and the obtained crude product is separated and purified by column chromatography to obtain the target product.

[0037] The reaction equation for the above catalytic diazo-nitrogen-hydrogen insertion reaction of amines is shown below:

[0038]

[0039] Wherein, R2 is one of methyl, ethyl, isopropyl, tert-butyl or benzyl;

[0040] R3 is a phenyl group substituted with a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom at the para position and a hydrogen atom or a chlorine atom at the meta position;

[0041] R4 is a phenyl group whose para position is substituted with a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a trifluoromethyl group, whose meta position is substituted with a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and whose ortho position is substituted with a hydrogen atom or a methyl group.

[0042] In the above formula III, [Au] represents the binuclear gold catalyst.

[0043] Preferably, the amount of the amine compound used is 1 to 10 molar equivalents of the diazo compound, preferably 2 to 8 molar equivalents.

[0044] Preferably, the solvent in the solution during the reaction is at least one of ethyl acetate, dichloromethane, 1,2-dichloroethane, chloroform, toluene, acetonitrile or tetrahydrofuran.

[0045] Preferably, the concentration of the reactants is 0.1 to 10 M, such as 1 to 9 M (M represents mol / L).

[0046] Preferably, the reaction temperature is 10-100°C.

[0047] Preferably, the reaction time is 0.1 to 48 hours.

[0048] Preferably, the steps of the cycloaddition reaction of the enyne aldehyde are as follows:

[0049] In a nitrogen atmosphere, a solution of an enyne aldehyde compound, a solution of an ethylene compound and a solution of the binuclear gold catalyst are added to a reactor, and the mixture is stirred to react. After the reaction, the solvent is removed from the reaction solution by vacuum distillation to a constant weight, and the crude product is separated and purified by column chromatography to obtain the target product.

[0050] The reaction equation of the above enyne aldehyde cycloaddition reaction is shown below:

[0051]

[0052] wherein R5 is a phenyl group whose para position is substituted with a hydrogen atom, a methyl group, a tert-butyl group, a methoxy group, a fluorine atom or an N-morpholinyl group, whose meta position is substituted with a hydrogen atom or a methyl group, and whose ortho position is substituted with a hydrogen atom or a methyl group;

[0053] R6 is a phenyl group whose para position is substituted with a hydrogen atom, a methyl group, a tert-butyl group, an allyl group, a phenyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom or a trifluoromethyl group, whose meta position is substituted with a hydrogen atom, a methyl group or a chlorine atom, and whose ortho position is substituted with a hydrogen atom, a methyl group or a chlorine atom.

[0054] In the above formula IV, [Au] represents the binuclear gold catalyst.

[0055] Preferably, the R5 may also be n-hexyl.

[0056] Preferably, the R6 may also be one of β-naphthyl, cyclohexyl and ethoxy.

[0057] Preferably, the amount of the ethylene compound used is 1 to 10 molar equivalents of the enyne aldehyde compound, for example 2 to 8 molar equivalents.

[0058] Preferably, the solvent in the solution is at least one of dichloromethane, 1,2-dichloroethane, chloroform, toluene, acetonitrile or tetrahydrofuran.

[0059] Preferably, the concentration of the reactants is 0.1-10M, such as 1-9M.

[0060] Preferably, the reaction temperature is 10-100°C.

[0061] Preferably, the reaction time is 0.1 to 48 hours.

[0062] Preferably, the steps of the cyclization reaction of the enynyl ketone are as follows:

[0063] In a nitrogen atmosphere, a solution of an enynyl ketone compound, a solution of a nucleophilic reagent (alcohol or imine ester), a solution of a binuclear gold catalyst and a base are added to a reactor, and the mixture is stirred to react. After the reaction is completed, the solvent is removed from the reaction solution by vacuum distillation to a constant weight, and the crude product is separated and purified by column chromatography to obtain the target product.

[0064] The reaction equation of the cyclization reaction of the above enynone is as follows:

[0065]

[0066] wherein R7 is a phenyl group whose para position is substituted with a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, an allyl group, a phenyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group or an acetyl group, whose meta position is substituted with a hydrogen atom or a methyl group, and whose ortho position is substituted with a hydrogen atom or a fluorine atom;

[0067] R8 is one of methyl, ethyl, isopropyl, n-butyl, tert-butyl, allyl, propargyl, phenylallyl and phenylpropargyl.

[0068] R9 is a hydrogen atom or an ethoxy group;

[0069] Preferably, the R7 may also be one of α-naphthyl, β-naphthyl and n-octyl.

[0070] Preferably, R8 may also be a phenyl group substituted with a hydrogen atom, methyl, methoxy, bromine, trifluoromethyl, nitro or nitrile group at the para position, a hydrogen atom or methyl group at the meta position, and a hydrogen atom or methyl group at the ortho position.

[0071] Preferably, the nucleophile is an alcohol or an imine ester.

[0072] Preferably, the amount of the nucleophile used is 1 to 10 molar equivalents of the enynyl ketone compound, for example 2 to 8 molar equivalents.

[0073] Preferably, the base is used in an amount of 1 to 10 molar equivalents of the enynone compound, such as 2 to 8 molar equivalents.

[0074] Preferably, the base is at least one of an inorganic base (sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate) or an organic base (triethylamine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene).

[0075] Preferably, the solvent in the solution is at least one of ethyl acetate, dichloromethane, 1,2-dichloroethane, chloroform, n-hexane, cyclohexane, toluene, acetonitrile or tetrahydrofuran.

[0076] Preferably, the concentration of the reactants is 0.1-10M, such as 1-9M.

[0077] Preferably, the reaction temperature is 10-100°C.

[0078] Preferably, the reaction time is 0.1 to 48 hours.

[0079] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0080] (1) The binuclear gold catalyst of the present invention has gold atoms and diphosphine ligands as the basic framework and has structural diversity.

[0081] (2) The preparation method of the binuclear gold catalyst of the present invention uses commercially available products as initial raw materials, and the product can be obtained in one step, which is simple to operate and has high reaction efficiency.

[0082] (3) The binuclear gold catalyst of the present invention can be used to catalyze the nitrogen-hydrogen insertion reaction of diazo and amine, the cycloaddition reaction of enyne aldehyde and the cyclization reaction of enyne ketone. In the above applications, the binuclear gold catalyst exhibits good stability and high tolerance to water, has high catalytic efficiency and novel reaction selectivity, and has a high product yield. DETAILED DESCRIPTION

[0083] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0084] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0085] The raw materials used in the examples are all conventional raw materials in the art, and the purity specifications of the raw materials used are analytically pure or chemically pure.

[0086] Example 1: Preparation of binuclear gold catalyst C1

[0087] The structural formula of the binuclear gold catalyst C1 (Ph in the structural formula represents a phenyl group) is:

[0088]

[0089] The reaction equation and preparation process of binuclear gold catalyst C1 are as follows:

[0090]

[0091] 76.9 mg of bis(diphenylphosphinothane) ligand (Ⅱ-A) was added to a dichloromethane suspension (10 mL) containing 58.9 mg of chloro(dimethylsulfide)gold, and then 177.2 mg of sodium tetrakis(3,5-di(trifluoromethyl)phenyl)borate was added. The mixture was stirred for 30 minutes and filtered through diatomaceous earth to remove the precipitate. The solvent was removed under reduced pressure to constant weight, and a small amount of dichloromethane was added to dissolve all the solids. N-pentane was added to precipitate the product. The resulting precipitate was washed with n-pentane and dried under vacuum to obtain binuclear gold catalyst C1.

[0092] The NMR and mass spectrometry characterization results of binuclear gold catalyst C1 are as follows: 1 H NMR (500MHz, DMSO-d6) δ7.90 (s, 8H), 7.63 (d, J = 12.5Hz, 12H), 7.51 (t, J = 7.3Hz, 4H), 7.45 (t, J = 7.5Hz, 8H), 5.02 (s, 2H). 13 CNMR(125MHz,DMSO-d6)δ162.0,161.6,161.2,160.8,134.5,134.0,132.8,129.7,129.3,129.0, 128.8,128.5,127.6,125.5,123.3,121.1,117.9,40.5,40.3,40.1,40.0,39.8,39.6,39.5,26.5.31 P NMR (203 MHz, DMSO-d6) δ 35.81. 19 F NMR(470MHz,DMSO-d6)δ-61.65.HRMS(ESI,m / z)calcd for C 50 H 44 P4Au2[M] 2+ :581.0857,found:581.0857.

[0093] Example 2: Preparation of binuclear gold catalyst C2

[0094] The structural formula of binuclear gold catalyst C2 (Ph in the structural formula represents phenyl) is:

[0095]

[0096] The preparation of binuclear gold catalyst C2 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0097] The NMR and mass spectrometry characterization results of binuclear gold catalyst C2 are as follows: 1 H NMR (500MHz, DMSO-d6) δ7.79(s,8H),7.62(s,10H),7.55(t,J=7.5Hz,4H),7.42(t,J=7.6Hz,8H),3.50(m,4H). 13 CNMR(125MHz,DMSO-d6)δ162.8,162.4,162.0,161.6,135.2,133.9,133.8,133.4,132.8,131.0,130. 5,130.4,129.9,129.7,129.6,129.4,129.2,128.3,126.1,124.0,121.8,118.3,118.2,117.8,22.6. 31 P NMR (203 MHz, DMSO-d6) δ 38.12. 19 F NMR(470MHz,DMSO-d6)δ-61.96.HRMS(ESI,m / z)calcd for C 52 H 48 P4Au2[M] 2+ :595.1013,found:595.1015.

[0098] Example 3: Preparation of binuclear gold catalyst C3

[0099] The structural formula of binuclear gold catalyst C3 (Ph in the structural formula represents phenyl) is:

[0100]

[0101] The preparation of binuclear gold catalyst C3 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0102] The NMR and mass spectrometry characterization results of binuclear gold catalyst C3 are as follows: 1 H NMR (500MHz, DMSO-d6) δ7.85 (s, 8H), 7.73 (s, 4H), 7.65–7.56 (m, 20H), 3.08 (d, J = 9.3Hz, 4H), 2.08 (s, 2H). 13 C NMR (125MHz, DMSO-d6) δ162.8,162.4,162.0,161.6,135.2,133.9,133.0,130. 2,129.6,129.4,129.1,128.3,126.1,123.9,121.8,118.2,117.8,28.3,23.5. 31 P NMR (203 MHz, DMSO-d6) δ 39.92. 19 FNMR(470MHz,DMSO-d6)δ-63.21.HRMS(ESI,m / z)calcd for C 54 H 52 P4Au2[M] 2+ :609.1170,found:609.1173.

[0103] Example 4: Preparation of binuclear gold catalyst C4

[0104] The structural formula of binuclear gold catalyst C4 is:

[0105]

[0106] The preparation of binuclear gold catalyst C4 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0107] The NMR and mass spectrometry characterization results of binuclear gold catalyst C4 are as follows: 1 H NMR (500MHz, DMSO-d6) δ7.85(s,8H),7.72(s,4H),7.66–7.52(m,20H),2.94(s,4H),1.86(m,4H). 13C NMR(125MHz,DMSO-d6)δ162.8,162.4,162.0,161.6,135.2,133.8,132.8,130.1,129.9,1 29.7,129.6,129.4,129.2,128.3,126.1,124.0,121.8,118.3,118.2,117.8,26.8,26.6. 31 P NMR (203 MHz, DMSO-d6) δ 42.40. 19 F NMR(470MHz,DMSO-d6)δ-63.20.HRMS(ESI,m / z)calcd for C 56 H 52 P4Au2[M] 2+ :623.1326,found:623.1329.

[0108] Example 5: Preparation of binuclear gold catalyst C5

[0109] The structural formula of binuclear gold catalyst C5 is:

[0110]

[0111] The preparation of binuclear gold catalyst C5 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0112] The NMR and mass spectrometry characterization results of binuclear gold catalyst C5 are as follows: 1 H NMR (500MHz, DMSO-d6) δ7.78–7.71(m,8H),7.63(d,J=7.4Hz,16H),7.52(t,J=7.6Hz,8H),6.65(m,2H). 13 C NMR(125MHz,DMSO-d6)δ162.0,161.6,161.2,160.8,150.1,135.3,135.2,134.5,133.5,130.0,129.3,129.1,129.0, 128.8,128.5,127.6,125.5,124.9,124.8,123.3,121.1,117.9,40.4,40.3,40.2,40.1,40.0,39.9,39.8,39.6,39.4. 31 P NMR (203 MHz, DMSO-d6) δ 43.30. 19 F NMR(470MHz,DMSO-d6)δ-61.98.HRMS(ESI,m / z)calcd for C52 H 44 P4Au2[M] 2+ :593.0857,found:593.0860.

[0113] Example 6: Preparation of binuclear gold catalyst C6

[0114] The structural formula of binuclear gold catalyst C6 is:

[0115]

[0116] The preparation of binuclear gold catalyst C6 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0117] The NMR and mass spectrometry characterization results of binuclear gold catalyst C6 are as follows: 1 H NMR (500MHz, DMSO-d6) δ7.80(m,8H),7.63(s,10H),7.39(t,J=7.7Hz,4H),7.14(t,J=7.4Hz,8H),3.59(m,2H),2.51(s,6H). 13 CNMR(125MHz,DMSO-d6)δ163.0,162.9,162.5,162.1,136.9,135.9,135.8,135.7,135.3,135. 2,134.8,134.4,134.3,134.2,134.1,133.6,133.5,132.3,132.2,132.1,131.7,131.4,131.3 ,131.1,131.0,130.9,130.7,130.4,130.3,130.1,129.9,129.8,129.6,129.4,129.3,129.2,129.0,128.9,128.7,126.5,124.4,122.2,118.7,118.6,118.2,55.2,14.7,14.5,14.4,14.2. 31 P NMR (203 MHz, DMSO-d6) δ 41.20. 19 F NMR(470MHz,DMSO-d6)δ-63.17.HRMS(ESI,m / z)calcd for C 56 H 56 P4Au2[M] 2+ :623.1326,found:623.1317.

[0118] Example 7: Preparation of binuclear gold catalyst C7

[0119] The structural formula of binuclear gold catalyst C7 is:

[0120]

[0121] The preparation of binuclear gold catalyst C7 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was The NMR and mass spectrometry characterization results of binuclear gold catalyst C7 are as follows: 1 HNMR(500MHz,DMSO-d6)δ7.96–7.24(m,26H),7.15–6.99(m,4H),3.31(s,6H),3.19(m,4H). 13 CNMR(125MHz,DMSO-d6)δ166.8,166.4,166.0,165.6,165.5,139.2,137.8,137.6,134.6,134.0,133.8,133.5,13 3.3,132.4,130.2,128.1,126.7,125.9,122.6,117.4,60.6,45.2,45.0,44.9,44.8,44.7,44.6,44.5,44.4,44.2. 31 P NMR (203 MHz, DMSO-d6) δ 29.79. 19 F NMR(470MHz,DMSO-d6)δ-62.03.HRMS(ESI,m / z)calcd for C 56 H 56 P4Au2[M] 2+ :655.1225,found:655.1229.

[0122] Example 8: Preparation of binuclear gold catalyst C8

[0123] The structural formula of binuclear gold catalyst C8 is:

[0124]

[0125] The preparation of binuclear gold catalyst C8 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0126] The NMR and mass spectrometry characterization results of binuclear gold catalyst C8 are as follows: 1H NMR (500MHz, DMSO-d6) δ7.76(s,4H),7.67(t,J=3.2Hz,8H),7.60(t,J=7.4Hz,2H),7.44(m,8H),7.28(t,J= 7.4Hz,2H),7.10(d,J=7.6Hz,4H),6.83(d,J=7.6Hz,4H),3.91(s,2H),3.45(d,J=10.5Hz,2H),2.39(m,8H). 13 C NMR (125MHz, DMSO-d6) δ162.1,161.7,161.3,160.9,139.8,134.5,133.3,129.8,129.4,129.2,129.0,128.7,128.5,128.1,128.0,127 .7,127.6,125.4,123.3,121.1,117.6,79.3,79.0,78.8,54.8,47.4,46.7,40.1,39.9,39.8,39.6,39.4,39.3,39.1,34.1,31.2,17.7. 31 P NMR (203 MHz, DMSO-d6) δ 62.40. 19 F NMR(470MHz,DMSO-d6)δ-61.66.HRMS(ESI,m / z)calcd for C 68 H 72 P4Au2[M] 2+ :703.1952,found:703.1955.

[0127] Example 9: Preparation of binuclear gold catalyst C9

[0128] The structural formula of binuclear gold catalyst C9 is:

[0129]

[0130] The preparation of binuclear gold catalyst C9 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0131] The NMR and mass spectrometry characterization results of binuclear gold catalyst C9 are as follows: 1 H NMR (500MHz, DMSO-d6) δ7.59–7.04(m,22H),6.78(m,4H),2.67(m,2H),2.00–1.94(m,2H),1.82(dd,J=9.6Hz,2H),1.62(m,2H). 13C NMR (125MHz, DMSO-d6) δ151.4,148.6,135.5,134.3,133.8,132.3,131.7,129.9,128.7,121.7,119.2,117.8,65.2,40.6,31.3,29.9. 31 P NMR (203 MHz, DMSO-d6) δ 44.05. 19 FNMR(470MHz,DMSO-d6)δ-80.08.HRMS(ESI,m / z)calcd for C 82 H 68 P4Au2[M] 2+ :785.1796,found:785.1793.

[0132] Example 10: Preparation of binuclear gold catalyst C10

[0133] The structural formula of binuclear gold catalyst C10 is:

[0134]

[0135] The preparation of binuclear gold catalyst C10 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0136] The NMR and mass spectrometry characterization results of binuclear gold catalyst C10 are as follows: 1 H NMR (500MHz, DMSO-d6) δ7.80–7.24(m,36H),7.03(t,J=7.6Hz,2H),6.42(d,J=7.7Hz,2H). 13 C NMR(125MHz,DMSO-d6)δ162.8,162.3,162.0,161.9,136.1,135.7,135.2,134.4,13 3.9,133.7,131.8,130.7,130.5,129.6,128.6,128.3,126.1,123.9,118.2,117.9. 31 P NMR (203 MHz, DMSO-d6) δ 40.96. 19 F NMR(470MHz,DMSO-d6)δ-63.24.HRMS(ESI,m / z)calcd for C 72 H 56 P4Au2[M] 2+ :719.1326,found:719.1329.

[0137] Example 11: Preparation of binuclear gold catalyst C11

[0138] The structural formula of binuclear gold catalyst C11 is:

[0139]

[0140] The preparation of binuclear gold catalyst C11 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0141] The NMR and mass spectrometry characterization results of binuclear gold catalyst C11 are as follows: 1 H NMR(500MHz,DMSO-d6)δ7.62(t,J=6.9Hz,6H),7.47–7.40(m,6H),7.26(m,8H),7.06(t ,J=8.0Hz,2H),6.98–6.93(m,2H),6.52–6.44(m,2H),4.16–3.94(m,4H),1.66(m,2H). 13 C NMR (125MHz, DMSO-d6) δ159.9,135.3,135.0,134.5,133.5,133.0,132.1,131. 4,130.7,130.4,129.8,129.4,128.0,126.2,123.8,119.9,117.9,73.6,29.1. 31 P NMR (203 MHz, DMSO-d6) δ 40.23. 19 F NMR(470MHz,DMSO-d6)δ-75.17.HRMS(ESI,m / z)calcd for C 78 H 64 P4Au2[M] 2+ :791.1538,found:791.1543.

[0142] Example 12: Preparation of binuclear gold catalyst C12

[0143] The structural formula of binuclear gold catalyst C12 is:

[0144]

[0145] The preparation of binuclear gold catalyst C12 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0146] The NMR and mass spectrometry characterization results of binuclear gold catalyst C12 are as follows: 1H NMR (500MHz, DMSO-d6) δ7.62 (s, 10H), 7.48 (m, 4H), 7.40 (d, J = 10.8Hz, 6H), 7.31 (t, J =7.6Hz,2H),7.23(m,9H),7.14(t,J=7.6Hz,5H),6.53(m,2H),6.38(d,J=8.2Hz,2H). 13 C NMR (125MHz, DMSO-d6) δ162.3,161.9,161.5,161.1,151.1,148.7,134.9,134.7,134.3,133.5 ,132.9,129.9,129.1,129.0,128.8,128.7,128.5,127.7,127.4,127.3,125.6,123.4,121.27 119.3,117.4,116.6,109.4,102.2,77.2,77.0,76.7. 31 P NMR (203 MHz, DMSO-d6) δ 41.13. 19 FNMR(470MHz,DMSO-d6)δ-63.24.HRMS(ESI,m / z)calcd for C 76 H 56 P4Au2[M] 2+ :807.1123,found:807.1118.

[0147] Example 13: Preparation of binuclear gold catalyst C13

[0148] The structural formula of binuclear gold catalyst C13 is:

[0149]

[0150] The preparation of binuclear gold catalyst C13 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0151] The NMR and mass spectrometry characterization results of binuclear gold catalyst C13 are as follows: 1 H NMR(500MHz,DMSO-d6)δ8.05(d,J=7.0Hz,6H),7.53(d,J=7.5Hz,10H),7.44(t,J=7.6Hz,5H),7.28(m,3H),7.21 (t,J=7.6Hz,2H),7.08(d,J=8.1Hz,2H),6.73(d,J=8.2Hz,4H),6.54(t,J=6.6Hz,4H),1.77(m,8H),1.54(m,8H).13 C NMR (125MHz, DMSO-d6) δ163.1,162.7,162.3,161.9,144.4,139.8,135.6,135.5,133.8,133.2,131.1,130.4,130.0,129.9,129.7,129.5,128. 6,127.9,127.7,127.5,126.4,124.3,123.2,122.1,118.7,118.5,55.2 ,40.8,40.6,40.4,40.3,40.1,30.1,28.1,27.9,23.0,22.7,22.4,22.1. 31 P NMR (203 MHz, DMSO-d6) δ 46.23. 19 FNMR(470MHz,DMSO-d6)δ-57.80.HRMS(ESI,m / z)calcd for C 88 H 80 P4Au2[M] 2+ :827.2265,found:827.2211.

[0152] Example 14: Preparation of binuclear gold catalyst C14

[0153] The structural formula of binuclear gold catalyst C14 is:

[0154]

[0155] The preparation of binuclear gold catalyst C14 was carried out in the same manner as in Example 1, except that the added bisphosphine ligand was

[0156] The NMR and mass spectrometry characterization results of binuclear gold catalyst C14 are as follows: 1 H NMR(500MHz,Chloroform-d)δ7.74(t,J=3.3Hz,8H),7.63(t,J=7.4Hz,2H),7.52(d,J=16.4Hz,10H),7.44(d,J=6.4Hz,5H),7.39(t,J=7.5Hz, 3H), 7.12 (t, J = 4.5Hz, 2H), 7.04 (t, J = 7.5Hz, 2H), 6.92 (t, J = 7.7Hz, 2H), 6.82 (d, J = 6.7Hz, 4H), 6.74 (t, J = 7.6Hz, 4H), 6.37 (d, J = 8.6Hz, 2H). 13C NMR(125MHz,Chloroform-d)δ162.3,161.9,161.5,161.1,141.4,134.8,134.1,133.8,133.5,133.1,132.4,130.3,130.2,129.4,129. 3,129.1,129.0,128.8,128.6,128.3,128.2,127.8,127.6,126.4,125.6,125.4,125.2,124.9,123.4,121.3,117.5,77.2,77.0,76.7. 31 PNMR(203MHz,Chloroform-d)δ41.04. 19 F NMR(470MHz,Chloroform-d)δ-62.37.HRMS(ESI,m / z)calcd for C 88 H 64 P4Au2[M] 2+ :819.1639,found:819.1643.

[0157] Example 15: Catalytic Nitrogen Hydrogen Insertion Reaction

[0158] The binuclear gold catalyst catalyzes the nitrogen-hydrogen insertion reaction, and the reaction equation (C14 in the reaction equation represents the binuclear gold catalyst C14 prepared in Example 14) and the reaction steps are as follows:

[0159]

[0160] Under a nitrogen atmosphere, 35.2 mg of methyl 2-diazo-2-phenylacetate, 27.9 mg of aniline and 0.3 mg of binuclear gold catalyst C14 were added to a dry 25 mL Schlenk tube, and then 2 mL of 1,2-dichloroethane was added. The reaction solution was stirred at 40°C for 24 h. After the reaction was completed, the solvent was removed by reduced pressure distillation, and the crude product was separated and purified by column chromatography to obtain the target product. The yield of the target product was 89% (the actual yield of the target product / the theoretical yield of the target product*100% is the actual yield of the target product, that is, 89% here is the actual yield of the target product).

[0161] The NMR characterization results of the above target product are: 1H NMR(500MHz,Chloroform-d)δ7.59–7.46(m,2H),7.44–7.27(m,3H),7.19–7.05 (m,2H),6.72(t,J=7.3Hz,1H),6.59(d,J=7.9Hz,2H),5.11(s,1H),3.75(s,3H). 13 C NMR (125MHz, Chloroform-d) δ172.3,145.9,137.6,129.2,128.9,128.3,127.2,118.1,113.4,60.7,52.8.

[0162] Example 16: Catalytic Cycloaddition Reaction

[0163] The binuclear gold catalyst catalyzes the cycloaddition reaction, and the reaction equation (C14 in the reaction equation represents the binuclear gold catalyst C14 prepared in Example 14) and the reaction steps are as follows:

[0164]

[0165] In a nitrogen atmosphere, 41.2 mg of 2-phenylethynylbenzaldehyde, 104.2 mg of styrene and 3.3 mg of binuclear gold catalyst C14 were added to a dry 25 mL Schlenk tube, and then 2 mL of 1,2-dichloroethane was added. The reaction solution was stirred at 100° C. for 12 h. After the reaction was completed, the solvent was removed by reduced pressure distillation. The crude product was separated and purified by column chromatography to obtain the target product. The yield of the target product was 82%.

[0166] The NMR characterization results of the above target product are: 1 H NMR(500MHz,Chloroform-d)δ7.84–7.72(m,2H),7.50–7.43(m,2H),7.28(dd,J=14.5,7.4Hz,2H ),7.19–7.11(m,8H),7.07–6.96(m,6H),6.96–6.86(m,4H),6.81–6.74(m,2H),6.68–6.61(m,1H) ,6.53(d,J=7.7Hz,1H),5.23(d,J=5.9Hz,1H),3.80(d,J=7.0Hz,1H),3.73–3.56(m,1H),3.34(m, 1H),3.14(m,1H),3.01(dd,J=16.6,6.6Hz,1H),2.84(dd,J=16.6,4.3Hz,1H),2.18–2.07(m,1H). 13C NMR(125MHz,Chloroform-d)δ202.0,199.5,142.1,140.9,138.6,138.1,137.6,137.4,136.5,135.8,135.2,133.3,133.2,132.3,131.4,12 9.3,129.3,128.5,128.4,128.3,128.2,128.1,127.7,127.6,127.1,1 27.0,126.8,126.2,126.1,125.3,51.0,43.4,39.8,39.0,33.1,25.4.

[0167] Example 17: Catalytic Cycloaddition Reaction

[0168] The binuclear gold catalyst catalyzes the cycloaddition reaction, and the reaction equation (C1 in the reaction equation represents the binuclear gold catalyst C1 prepared in Example 1) and the reaction steps are as follows:

[0169]

[0170] In a nitrogen atmosphere, 41.2 mg of 2-phenylethynylbenzaldehyde, 104.2 mg of styrene and 2.9 mg of binuclear gold catalyst C1 were added to a dry 25 mL Schlenk tube, and then 2 mL of 1,2-dichloroethane was added. The reaction solution was stirred at 100° C. for 12 h. After the reaction was completed, the solvent was removed by reduced pressure distillation. The crude product was separated and purified by column chromatography to obtain the target product. The yield of the target product was 88%.

[0171] The NMR characterization results of the above target product are: 1 H NMR(500MHz,Chloroform-d)δ7.87(d,J=7.7Hz,2H),7.45(t,J=7.4Hz,1H),7.34–7.26(m,5H),7. 21(m,3H),7.14(m,2H),7.02(d,J=7.7Hz,1H),3.12(t,J=7.9Hz,2H),2.91(t,J=9.2,6.7Hz,2H). 13 C NMR(125MHz,Chloroform-d)δ199.71,140.92,139.51,137.32,135.06,134.71,133.26,133.14,12 9.41,128.36,128.15,127.65,127.63,127.58,126.84,125.17,77.29,77.04,76.78,29.94,28.32.

[0172] The above only gives the catalytic effects of binuclear gold catalysts prepared in some embodiments in specific catalytic reactions. The catalytic effects of binuclear gold catalysts prepared in other embodiments are similar to that of binuclear gold catalyst C14.

[0173] The above description is only a preferred embodiment of the present invention and does not limit the protection scope of the present invention in any form. Any technician familiar with the profession, without departing from the scope of the technical solution of the present invention, according to the technical essence of the present invention, any simple modification, equivalent replacement and improvement made to the above embodiment still falls within the protection scope of the technical solution of the present invention.

Claims

1. A binuclear gold catalyst, characterized in that The binuclear gold catalyst is selected from any one of the following structures:

2. The method for preparing the binuclear gold catalyst according to claim 1, characterized in that: The following steps are involved: Adding a diphosphine ligand to a solution containing a gold source, and then adding a salt containing an X group to react and precipitate to obtain the binuclear gold catalyst; The X group in the X-group-containing salt is tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

3. The preparation method according to claim 2, characterized in that: The reaction temperature is 5 to 100° C.; the reaction time is 0.1 to 48 hours.

4. The preparation method according to claim 2, characterized in that: The gold source is chloro(dimethyl sulfide)gold and / or chloro(tetrahydrothiophene)gold; the salt containing the X group is a sodium salt, a lithium salt or a silver salt containing the X group.

5. Use of the binuclear gold catalyst according to claim 1 in catalyzing the nitrogen-hydrogen insertion reaction of diazo and amine, the cycloaddition reaction of enyne aldehyde or the cyclization reaction of enyne ketone.

6. The use according to claim 5, characterized in that: The steps of catalyzing the nitrogen-hydrogen insertion reaction of diazo and amine are as follows: In a nitrogen atmosphere, a solution of a diazo compound, a solution of an amine compound and a solution of the binuclear gold catalyst are added to a reactor, and the mixture is stirred to react. After the reaction, the solvent is removed from the reaction solution by vacuum distillation to a constant weight, and the crude product is separated and purified by column chromatography to obtain the target product.

7. The use according to claim 5, characterized in that: The steps of the cycloaddition reaction of the enyne aldehyde are as follows: In a nitrogen atmosphere, a solution of an enyne aldehyde compound, a solution of an ethylene compound and a solution of the binuclear gold catalyst are added to a reactor, and the mixture is stirred to react. After the reaction, the solvent is removed from the reaction solution by vacuum distillation to a constant weight, and the crude product is separated and purified by column chromatography to obtain the target product.

8. The use according to claim 5, characterized in that: The steps of the cyclization reaction of the enynone are as follows: In a nitrogen atmosphere, a solution of an enynyl ketone compound, a solution of a nucleophilic reagent, a solution of a binuclear gold catalyst and a base are added to a reactor, and the mixture is stirred to react. After the reaction is completed, the solvent is removed from the reaction solution by vacuum distillation to a constant weight, and the crude product is separated and purified by column chromatography to obtain the target product.

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