Supported cluster catalyst and its application in ketone alkynylation reaction

Abstract

The application discloses a supported cluster catalyst and application of the supported cluster catalyst in a ketone alkinylization reaction, wherein a molecular formula of the supported cluster catalyst is Pt1Ag 24 / CNT or Ag 25 / CNT; wherein Pt1Ag 24 The molecular formula of the nanocluster is Pt1Ag 24 (SPhMe2) 18 (PPh4)2, abbreviated as Pt1Ag 24 ; Ag 25 The molecular formula of the nanocluster is Ag 25 (SPhMe2) 18 PPh4, abbreviated as Ag 25 The application discloses a supported cluster catalyst and application of the supported cluster catalyst in a ketone alkinylization reaction, wherein a molecular formula of the supported cluster catalyst is Pt1Ag 24 / CNT and Ag 25 The Pt1Ag / CNT and Ag / CNT catalysts can efficiently catalyze the alkinylization reaction of ketones under mild conditions, the catalysts can be recycled at least three times, the activity of the catalysts is not reduced, and the substrates have wide universality and good practicability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic catalytic synthesis, and particularly relates to a supported cluster catalyst and application thereof in ketone alkinylization reaction. BACKGROUND

[0002] The addition reaction of ketone and terminal alkyne is a kind of important organic synthesis reaction. The product propargyl alcohol not only has wide biological activity and pharmacological activity, but also is an important component for synthesizing heterocyclic and complex components. As a special electron-withdrawing group, the trifluoromethyl group plays an important role in biological drugs. Because the incorporation of fluorine or fluorine-containing groups into organic molecules can lead to improved pharmacological properties, so that the organic molecules have higher reactivity, lipophilicity and biological activity. However, naturally occurring fluorinated compounds are almost nonexistent in nature. Therefore, it is of great significance to introduce CF3 group into organic reactions.

[0003] Improving the understanding of the relationship between structure and property is the basis of catalysis. Metal nanoclusters are usually composed of metal skeletons and organic ligands with precise atom number. The modification of metal and organic ligands provides a strategy for efficient catalysis of surface composite sites of atomically precise metal nanoclusters. Improving the understanding of the relationship between structure and property is the basis of catalysis. In recent years, atomically precise metal nanoclusters (NCs) have ultra-small size, unique electronic structure and rich unsaturated active sites, and show high catalytic activity and unique selectivity in catalytic reactions. Zhu and his colleagues designed a core-free bimetallic nanocluster Au4Cu5 / AC, which showed higher activity than core-free monometallic nanoclusters (Au 11 / AC and Cu 11 / AC), core-shell nanoclusters (Au 25 / AC, Cu 25 / AC and Au1Cu 24 / AC) and single-atom catalysts (AuSAC and Cu SAC) in Ullmann C-O coupling reaction. (Nano Res, 2023, 16(8): 10756-10762) Jin group reported a series of atomically precise M1Ag 24 (SR) 18 NCs (M = Ag / Au / Pd / Pt), and studied the influence of single-atom doping on ORR catalytic activity. Experimental results show that in Ag 25The doping of Pd and Pt in the metal core of NC can reduce the initial potential, thereby improving the reaction activity. Single-atom doping can affect the performance of ORR by regulating the energy required to expose the surface active site and the energy required to form *OOH on the exposed active site. (J. Phys. Chem. C, 2021, 125, 24831-24836) In addition, homogeneous catalysts exhibit excellent catalytic activity due to their ability to fully contact the substrate, but at the same time, they are difficult to recover after the reaction, resulting in waste of resources. Therefore, it is necessary to use heterogeneous catalysts that are easy to recover and reuse. SUMMARY

[0004] The present application is directed to the problems existing in the prior art described above, and provides a supported cluster catalyst and its application in ketone alkinylization reaction. The supported cluster catalyst of the present application can efficiently catalyze the alkinylization reaction of ketones under mild conditions, and has excellent catalytic activity and stability. The activity of the catalyst does not decrease substantially after being used for several cycles, and has wide substrate universality.

[0005] The supported cluster catalyst of the present application has a molecular formula of Pt1Ag 24 / CNT or Ag 25 / CNT. The Pt1Ag 24 nanocluster has a molecular formula of Pt1Ag 24 (SPhMe2) 18 PPh4, and is abbreviated as Pt1Ag 24 ; Ag 25 The nanocluster has a molecular formula of Ag 25 (SPhMe2) 18 PPh4, and is abbreviated as Ag 25 .

[0006] The supported cluster catalyst of the present application is prepared by a method comprising the following steps:

[0007] Step 1: First, synthesize Pt1Ag 24 or Ag 25 nanocluster (Chem. Commun, 2017, 53, 9402.), which has a molecular formula of Pt1Ag 24 (SPhMe2) 18 PPh4, and is abbreviated as Pt1Ag 25 (SPhMe2) 18 PPh4, and is abbreviated as Pt1Ag 24 or Ag 25 nanocluster.

[0008] Step 2: uniformly disperse CNT in dichloromethane solution by ultrasonic treatment and stirring to obtain suspension A;

[0009] Step 3: Pt1Ag 24 or Ag 25 nanoclusters were added drop by drop into the suspension A obtained in step 2, and stirred for 4 h, and then Pt1Ag 24 / CNT or Ag 25 / CNT nanocomposites were obtained by centrifugation and drying.

[0010] The Pt1Ag 24 / CNT or Ag 25 / CNT catalysts of the present application, and the actual content of Ag in the nanocomposites is (0.3-0.5) wt%.

[0011] The application of the supported nanocluster catalysts in the catalysis of the alkenylation of ketones.

[0012] In the coupling reaction, the alkenyl compound and the ketone compound are used as raw materials, and the reaction is carried out in the presence of a base, a catalyst and a solvent.

[0013] The catalyst is Pt1Ag 24 / CNT or Ag 25 / CNT; the solvent is CH3CN, THF or DMF, preferably DMF; and the base is selected from K2CO3 and triethylamine, preferably potassium carbonate.

[0014] Further preferably, the alkenyl compound is 0.5 mmol, the ketone compound is 0.75 mmol, the amount of the base is 0.12 mmol, and the amount of the catalyst is 15 mg-30 mg, which are active in the alkenylation of ketones.

[0015] The alkenyl compound is selected from phenylacetylene or substituted phenylacetylene, and the substituted phenylacetylene includes 4-fluorophenylacetylene, 4-methylphenylacetylene, 4-methoxyphenylacetylene and the like.

[0016] The ketone compound is selected from trifluorophenylacetone, 4'-bromo-2,2,2-trifluorophenylacetone and the like.

[0017] The supported nanocluster catalysts of the present application have good catalytic activity for phenylacetylene and trifluorophenylacetone containing different substituents.

[0018] The beneficial effects of the present application are embodied in:

[0019] 1. The amount of catalyst used is small, and the reaction conditions are mild.

[0020] 2. The catalyst is simple to synthesize and prepare, has good catalytic activity, and has high atomic utilization rate.

[0021] 3、The material has good stability as a catalyst and can be recycled multiple times.

[0022] 4、The material has wide universality as a catalyst substrate. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 Pt1Ag 24 XPS and UV analysis spectrum of the nanocluster.

[0024] Figure 2 Pt1Ag 24 Crystal structure of the nanocluster.

[0025] Figure 3 Pt1Ag 24 TEM image of / CNT. DETAILED DESCRIPTION

[0026] The technical solutions of the present application will be further described below in combination with specific examples.

[0027] Example 1: Pt1Ag 24 Preparation of the nanocluster

[0028] Silver nitrate (30 mg, 0.18 mmol) and chloroplatinic acid hexahydrate (20 μL, 0.2 g / ml) were dissolved in a mixed solution of 2 mL of methanol and 20 mL of ethyl acetate, stirred for 15 min, 2,4-dimethylbenzenethiol (90 μL, 0.66 mmol) was added to the above solution, and stirring was continued for 15 min, and finally sodium borohydride (20 mg, 0.51 mmol) was added to the above solution. After the reaction was stopped, the solvent was spun dry, the product was extracted into a methanol solution and precipitated by adding tetraphenylphosphonium bromide, the precipitate was collected by centrifugation and dissolved in a small amount of CH2Cl2 solution, and stored in a single crystal bottle, the upper layer of the single crystal bottle was spread with a n-hexane solution (volume ratio of dichloromethane 1:3), a layer of ethanol reagent was spread in the middle, and after standing for 3 to 5 days, Pt1Ag 24 (SPhMe2) 18 (PPh4)2 nanocluster, referred to as Pt1Ag 24 Nanocluster. Figure 1 Pt1Ag 24 XPS and UV analysis spectrum of the nanocluster.

[0029] Example 2: Ag 25 Preparation of the nanocluster

[0030] AgNO3(37 mg, 0.22 mmol, dissolved in 2.5 mL CH3OH) was added to a 17 mL solution of dichloromethane to form a white precipitate. The reaction mixture was stirred for 20 minutes, then 2,4-dimethylbenzenethiol (90 μL, 0.66 mmol) and PPh4Br (6 mg, 0.014 mmol, dissolved in 0.5 mL CH3OH) were added and the reaction stirred for 20 min, the reaction solution changed from a colorless solution to a yellow cloudy liquid. The solution was stirred in an ice bath for 20 minutes, then 0.5 mL of freshly prepared NaBH4(30 mg / mL, 0.4 mmol) solution was added. The reaction was left overnight. The mixture in the organic phase was evaporated again under vacuum, then washed with methanol several times, and the final product was recrystallized from dichloromethane / hexane. After one week, Ag 25 nanocluster crystals were obtained.

[0031] Example 3: Preparation of Pt1Ag / CNT catalyst 24 Example 3: Preparation of Pt1Ag / CNT catalyst

[0032] The 200 mg CNT support was ultrasonically dispersed in 20 mL dichloromethane solution, then 2 mg Pt1Ag 24 nanocluster was dissolved in 10 mL dichloromethane solution and added dropwise to the above CNT solution. After stirring for 3 h, the stirring was stopped. The product was collected by centrifugation (10000 rpm) and washed with dichloromethane three times. Then the obtained catalyst was dried in an oven at 50 °C to obtain the supported Pt1Ag 24 nanocluster catalyst. The loading of the nanocluster was 0.3% wt by inductively coupled plasma emission spectrometer, and the catalyst was abbreviated as Pt1Ag / CNT. 24 nanocluster catalyst. The loading of the nanocluster was 0.3% wt by inductively coupled plasma emission spectrometer, and the catalyst was abbreviated as Pt1Ag / CNT. Figure 3 nanocluster catalyst. The loading of the nanocluster was 0.3% wt by inductively coupled plasma emission spectrometer, and the catalyst was abbreviated as Pt1Ag / CNT. 24 nanocluster catalyst. The loading of the nanocluster was 0.3% wt by inductively coupled plasma emission spectrometer, and the catalyst was abbreviated as Pt1Ag / CNT. 24 nanocluster catalyst. The loading of the nanocluster was 0.3% wt by inductively coupled plasma emission spectrometer, and the catalyst was abbreviated as Pt1Ag / CNT.

[0033] Example 4: Preparation of Ag / CNT catalyst 25 Example 4: Preparation of Ag / CNT catalyst

[0034] The 200 mg CNT support was ultrasonically dispersed in 20 mL dichloromethane solution, then 2 mg Pt1Ag 25nanoclusters were dissolved in 10 ml CH2Cl2, i.e. concentration of 0.2 mg / ml, and were added dropwise to the above stirring reaction flask, and the stirring was continued for 4 h, after which the solid was centrifuged and washed with CH2Cl2solution for 2-3 times. Finally, the obtained solid catalyst was placed in an oven set at 50 °C for about 3 h, and the desired catalyst was obtained, and the loading of the clusters was 0.3% wt, as tested by inductively coupled plasma emission spectrometer, and was denoted as Ag 25 / CNT.

[0035] Example 5: CNT catalyzed ketone alkynylation reaction

[0036] Into a dry Schlenk reaction flask, 0.5 mmol of phenylacetylene, 30 mg of CNT catalyst, 0.75 mmol of trifluorophenylacetylketone, 0.12 mmol of K2CO3 and 500 μL of DMF were added, and stirring was carried out under argon protection at 50 °C for 6 h. After the reaction was completed, the temperature of the reaction liquid was cooled to room temperature, and the reaction liquid and the solid catalyst were collected by centrifugation. The reaction liquid was analyzed by GC, and the yield was 1.1%.

[0037] Example 6: Pt1Ag 24 / CNT or Ag 25 / CNT catalyzed ketone alkynylation reaction (different catalysts)

[0038]

[0039] (1) Into a dry Schlenk reaction flask, 0.5 mmol of phenylacetylene, 30 mg of Pt1Ag 24 / CNT catalyst, 0.75 mmol of trifluorophenylacetylketone, 0.12 mmol of K2CO3 and 500 μL of DMF were added, and stirring was carried out under argon protection at 50 °C for 6 h. After the reaction was completed, the temperature of the reaction liquid was cooled to room temperature, and the reaction liquid and the solid catalyst were collected by centrifugation. The reaction liquid was analyzed by GC, and the yield was 1.1%.

[0040] 1 H NMR (400 MHz, CDC13) δ 7.87-7.80 (m, 2H), 7.55 (d, 2H), 7.39-7.28 (m, 6H), 3.23 (s, 1H) ppm; 13 C NMR (101 MHz, CDC13) δ 135.47, 132.21, 129.70, 128.62, 128.40, 127.35, 124.97, 122.13, 121.09, 88.21, 84.60, 73.67 ppm.

[0041] (2) Add 0.5 mmol phenylacetylene and 30 mg Ag 25 The reaction mixture, consisting of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate, and 500 μL DMF, was stirred at 50 °C for 6 h under argon protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product, with a yield of 60.0%.

[0042] Example 7: Pt1Ag 24 / CNT-catalyzed ketal ynylation reaction (different reaction solvents)

[0043] (1) Add 0.5 mmol phenylacetylene and 30 mg Pt1Ag 24 The reaction mixture of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate, and 500 μL CH3CN was stirred at 50 °C for 6 h under argon protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product with a yield of 18.2%.

[0044] (2) Add 0.5 mmol phenylacetylene and 30 mg Pt1Ag 24 The reaction mixture, consisting of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate, and 500 μL THF, was stirred at 50 °C for 6 h under argon protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product, with a yield of 10.5%.

[0045] Example 8: Pt1Ag 24 / CNT-catalyzed ketone acetylation reaction (depending on the type of base)

[0046] (1) Add 0.5 mmol phenylacetylene and 30 mg Pt1Ag 24 The reaction mixture of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol triethylamine, and 500 μL DMF was stirred at 50 °C for 6 h under argon protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product with a yield of 10.1%.

[0047] (2) Add 0.5 mmol phenylacetylene and 30 mg Pt1Ag24 / CNT catalyst, 0.75 mmol of trifluorophenylacetone, no base, 500 μL of DMF, stirring at 50 °C under argon for 6 h, after the reaction was completed, the reaction liquid was cooled to room temperature, the reaction liquid and solid catalyst were collected by centrifugation, the reaction liquid was analyzed by GC and the crude product was purified by silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product with a yield of 1.3%.

[0048] Example 9: Pt1Ag 24 / CNT catalyzed ketone-alkynyl reaction (different catalyst dosage)

[0049] (1) 0.5 mmol of phenylacetylene, 15 mg of Pt1Ag 24 / CNT catalyst, 0.75 mmol of trifluorophenylacetone, 0.12 mmol of potassium carbonate and 500 μL of DMF, stirring at 50 °C under argon for 6 h, after the reaction was completed, the reaction liquid was cooled to room temperature, the reaction liquid and solid catalyst were collected by centrifugation, the reaction liquid was analyzed by GC and the crude product was purified by silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product with a yield of 49.5%.

[0050] (2) 0.5 mmol of phenylacetylene, 20 mg of Pt1Ag 24 / CNT catalyst, 0.75 mmol of trifluorophenylacetone, 0.12 mmol of potassium carbonate and 500 μL of DMF, stirring at 50 °C under argon for 6 h, after the reaction was completed, the reaction liquid was cooled to room temperature, the reaction liquid and solid catalyst were collected by centrifugation, the reaction liquid was analyzed by GC and the crude product was purified by silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product with a yield of 73.2%.

[0051] Example 10: Pt1Ag 24 / CNT catalyzed ketone-alkynyl reaction (different reaction temperature)

[0052] (1) 0.5 mmol of phenylacetylene, 30 mg of Pt1Ag 24 / CNT catalyst, 0.75 mmol of trifluorophenylacetone, 0.12 mmol of potassium carbonate and 500 μL of DMF, stirring at 50 °C under argon for 6 h, after the reaction was completed, the reaction liquid was cooled to room temperature, the reaction liquid and solid catalyst were collected by centrifugation, the reaction liquid was analyzed by GC and the crude product was purified by silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product with a yield of 92.9%.

[0053] (2) 0.5 mmol of phenylacetylene, 30 mg of Pt1Ag 24Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst

[0054] Based on the above implementation cases, we selected the best reaction conditions (0.5 mmol of phenylacetylene, 30 mg of Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst 24 Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst 24 The stability of the Pt1Ag / CNT catalyst in the alkenylation reaction of ketones was tested, and the reaction results are shown in the following implementation cases.

[0055] Example 11: 30 mg of Pt1Ag / CNT catalyst, 0.5 mmol of phenylacetylene, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst 24 Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst

[0056] (1) 0.5 mmol of phenylacetylene, 30 mg of Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst 24 Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst

[0057] (2) 0.5 mmol of phenylacetylene, 30 mg of Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst 24 Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst

[0058] Recovery of Pt1Ag / CNT catalyst 24 Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst

[0059] Example 12: 30 mg of Pt1Ag / CNT catalyst, 0.5 mmol of phenylacetylene, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst 24 Pt1Ag / CNT catalyst, 0.75 mmol of trifluorophenylacetophenone, 0.12 mmol of potassium carbonate, 500 μL of DMF, under argon protection, the reaction temperature was 30 °C, the reaction time was 12 h or the reaction temperature was 50 °C, the reaction time was 6 h), to test the Pt1Ag / CNT catalyst

[0060] (1) Add 0.5 mmol phenylacetylene and 30 mg Pt1Ag 24 The reaction mixture, consisting of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate, and 500 μL DMF, was stirred at 50 °C for 6 h under argon protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product, with a yield of 91.7%.

[0061] (2) Add 0.5 mmol phenylacetylene and 30 mg Pt1Ag 24 The reaction mixture of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate, and 500 μL DMF was stirred at 30 °C for 12 h under argon protection. After the reaction was completed, the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product with a yield of 92.4%.

[0062] Example 13: Pt1Ag 24 / CNT-catalyzed ketal alkynylation reaction in three cycles

[0063] (1) Add 0.5 mmol phenylacetylene and 30 mg Pt1Ag 24 The reaction mixture, consisting of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate, and 500 μL DMF, was stirred at 50 °C for 6 h under argon protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product, with a yield of 91.2%.

[0064] (2) Add 0.5 mmol phenylacetylene and 30 mg Pt1Ag 24 The reaction mixture of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate and 500 μL DMF was stirred at 30 °C for 12 h under argon protection. After the reaction was completed, the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20) to obtain the main product with a yield of 91.4%.

[0065] The following implementation example is Pt1Ag 24 Substrate expansion for CNT-catalyzed ketone alkynylation reactions.

[0066]

[0067] Example 14: Pt1Ag24 / CNT-catalyzed ketynylation of 4-fluorophenylacetylene

[0068] 0.5 mmol 4-fluorophenylacetylene, 30 mg Pt1Ag 24 The reaction mixture, consisting of CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate, and 500 μL DMF, was stirred at 50 °C for 6 h under argon protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20), yielding the major product with a yield of 81.2%.

[0069] 1 H NMR (400MHz, CDCl3) δ7.83-7.82(m,2H),7.53-7.50(m,2H),7.48-7.41

[0070] (m,3H),7.09-7.05(m,2H),3.38(br,1H)ppm; 13 C NMR (101MHz, CDCl3) δ164.94,162.44,135.70,135.54,130.02,128.74,127.60,125.27,122.43,119.59,117.53,87.46,84.75,73.66ppm.

[0071] Example 15: Pt1Ag 24 / CNT-catalyzed ketynylation of 4-methylphenylacetylene

[0072] 0.5 mmol of 4-methylphenylacetylene and 30 mg of Pt1Ag were added. 24 The reaction mixture was prepared with CNT catalyst, 0.75 mmol trifluoroacetophenone, 0.12 mmol potassium carbonate and 500 μL DMF, and stirred at 50 °C for 6 h under argon protection. After the reaction was completed, the reaction solution was cooled to room temperature and the reaction solution and solid catalyst were collected by centrifugation. The crude product was purified by GC analysis and silica gel column chromatography (EtOAc / PE = 1:20), with a yield of 99.0%.

[0073] 1 H NMR (400MHz, CDCl3) δ7.86-7.80(m,2H),7.46-7.41(m,5H),7.19(d,2H),3.37(br,1H),2.40(s,3H)ppm; 13 C NMR (101MHz, CDCl3) δ139.70,135.36,131.78,129.27,

[0074] 129.03, 128.03, 127.05, 124.70, 121.86, 117.71, 88.11, 83.82, 73.07, 21.33 ppm.

[0075] Example 16: Pt1Ag 24 / CNT catalyzed ketovinylation of 4-methoxyphenylacetylene

[0076] 0.5 mmol of 4-methoxyphenylacetylene, 30 mg of Pt1Ag 24 / CNT catalyst, 0.75 mmol of 4'-bromo-2,2,2-trifluoroacetophenone, 0.12 mmol of potassium carbonate and 500 μL of DMF were stirred at 50 °C under argon for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The reaction solution was analyzed by GC and the crude product was purified by silica gel column chromatography (EtOAc / PE = 1:20), and the yield was 93.2%.

[0077] 1 HNMR (400 MHz, CDC13) δ 7.90-7.77 (m, 2H), 7.50-7.40 (m, 5H), 6.89 (d, 2H), 3.83 (s, 3H), 3.32 (s, 1H) ppm; 13 CNMR (101 MHz, CDC13)

[0078] δ 160.61, 135.70, 133.76, 129.57, 128.34, 127.44, 125.10, 122.20, 114.25, 113.13, 88.30, 83.42, 73.67, 55.49 ppm.

[0079] Example 16: Pt1Ag 24 / CNT catalyzed ketovinylation of 4-methoxyphenylacetylene

[0080] 0.5 mmol of 4-methoxyphenylacetylene, 30 mg of Pt1Ag 24 / CNT catalyst, 0.75 mmol of 4'-bromo-2,2,2-trifluoroacetophenone, 0.12 mmol of potassium carbonate and 500 μL of DMF were stirred at 50 °C under argon for 6 h. After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution and solid catalyst were collected by centrifugation. The reaction solution was analyzed by GC and the crude product was purified by silica gel column chromatography (EtOAc / PE = 1:20), and the yield was 93.2%.

[0081] 1H NMR (400 MHz, CDC13) δ 7.70 (d, 2H), 7.56-7.49 (m, 4H), 7.40-7.30 (m, 3H), 3.48 (br, 1H) ppm; 13 C NMR (101 MHz, CDC13) δ 134.91, 132.51, 131.88, 130.16, 129.44, 128.97, 127.85, 125.04, 124.44, 122.23, 121.12, 119.35, 88.93, 85.09, 73.05 ppm.

Claims

1. Use of a supported cluster catalyst in catalyzing the alkenylation of ketones, characterized in that: in the alkenylation of ketones, an alkenyl compound and a ketone compound are used as raw materials, and the reaction is carried out in the presence of a base, a supported cluster catalyst, and a solvent; The supported cluster catalyst is Pt1Ag 24 (SPhMe2) 18 (PPh4)2 / CNT, abbreviated as Pt1Ag 24 / CNT; the actual content of Ag in the supported cluster catalyst is (0.3-0.5) wt%; the solvent is DMF; the base is K2CO3; the alkenyl compound is selected from phenylacetylene or substituted phenylacetylene, and the substituted phenylacetylene includes 4-fluorophenylacetylene, 4-methylphenylacetylene, and 4-methoxyphenylacetylene; the ketone compound is selected from trifluorophenylacetone and 4'-bromo-2,2,2-trifluorophenylacetone.

2. The use according to claim 1, characterized in that: the amount of the alkenyl compound is 0.5 mmol, the amount of the ketone compound is 0.75 mmol, the amount of the base is 0.12 mmol, the amount of the catalyst is 15 mg-30 mg, and the reaction temperature is 30°C-50°C.

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