New type of copper cluster compound and its synthesis method and application in sonogashira reaction
By generating copper cluster compounds as catalysts and adjusting the charge properties of phosphorus ligands, the problem of the Sonogashira reaction being difficult to proceed rapidly under mild conditions was solved, achieving a highly efficient catalytic effect suitable for industrial production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HUNAN UNIV
- Filing Date
- 2022-03-30
- Publication Date
- 2026-07-10
AI Technical Summary
The existing Sonogashira reaction is difficult to carry out rapidly under mild conditions, and the stability and efficiency of the catalytic system need to be improved.
A copper cluster compound was generated by reacting R2PCF2H with CuI and used as a catalyst in the Sonogashira reaction. The charge properties of the phosphorus ligand were adjusted to accelerate the metal transfer step, thereby forming copper cluster molecules to enhance catalytic activity.
The Sonogashira reaction was achieved rapidly and efficiently at room temperature, with high yield, simple operation, and suitability for industrial production.
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Figure CN116284124B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of catalytic organic synthesis, specifically involving a novel class of copper cluster compounds and their synthetic methods, and applying them to the classic Sonogashira reaction. Background Technology
[0002] The Sonogashira reaction has been widely used in the synthesis of natural products, pharmaceutical molecules, agrochemicals, and organic functional materials containing endoys. Due to the importance of this reaction, scientists have made significant efforts to improve this catalytic system, including using other transition metals, ligand variations, copper-free methods, different solvents, and catalyst loading. However, in these pioneering works, reports of reactions occurring at room temperature for short durations (less than 15 minutes) are rare. This catalytic system can synthesize some complex pharmaceutical derivatives and natural products containing endoys.
[0003] To achieve a rapid Sonogashira reaction under mild conditions, we first investigated its reaction mechanism. The metal transfer step is generally considered the rate-determining step, therefore we sought to alter its rate by changing the charge of the functional groups attached to the phosphorus atom. We have already reported the R₂PCF₂H compound and its synthesis, and we envision applying it to the Sonogashira reaction. Furthermore, since the R₂PCF₂H compound is readily oxidized, we hoped it could form a metal complex. Summary of the Invention
[0004] This invention discloses a novel class of copper cluster compounds, their synthetic method, and their application in the Sonogashira reaction. The method uses R₂PCF₂H and CuI as reactants and THF as solvent to synthesize a novel class of copper cluster compounds at 100°C. Applying these copper cluster compounds to the Sonogashira reaction allows the reaction to proceed at room temperature for 1-20 minutes with high yields. This Sonogashira reaction method offers advantages such as mild conditions, rapid reaction rate, high yield, ease of operation, and easy scale-up, making it beneficial for industrial production.
[0005] To achieve rapid reactions under mild conditions, understanding the reaction mechanism is essential. The Lei Aiwen research group at Wuhan University demonstrated that the metal transfer step is the rate-determining step in this reaction. Therefore, we hypothesize that by modifying the groups on the phosphorus ligand to electron-withdrawing groups, the reaction can be enhanced by increasing the reaction rate. II (X)L nThe electrophilicity of the (L=PR3) complex may accelerate the nucleophilic attack process of the nucleophile copper-acetylene compound, thereby increasing the metal transfer rate. Furthermore, R2PCF2H is unstable in air and easily oxidized. Therefore, we hoped that this ligand could form a complex with a metal. Initial attempts were made to coordinate with palladium, but these failed. When copper was used for coordination, copper cluster molecules were found to form. Similar copper clusters have been reported in the literature for use in coupling reactions, where the ligand dissociates from the copper cluster in the reaction system and then coordinates with palladium, thereby enhancing the activity of the palladium catalyst.
[0006] Therefore, we applied copper clusters to the Sonogashira reaction and found that the reaction could be carried out rapidly and efficiently under mild conditions.
[0007]
[0008] To achieve the above-mentioned objectives, the present invention proposes the following technical solution:
[0009] A novel class of copper cluster compounds and their synthetic method, wherein the structural formulas of copper cluster compounds 1, 2, 3, and 4 are as follows:
[0010]
[0011] The compounds 1-4 are synthesized by reacting R2PCF2H(5) and CuI, wherein R is phenyl, 4-methylphenyl, naphthyl, or 3,5-dimethylphenyl.
[0012] In the above synthesis method, the structural formula of compound 5, which is the starting material R2PCF2H, is as follows:
[0013]
[0014] The compound 5 wherein R is selected from phenyl, 4-methylphenyl, naphthyl, 3,5-dimethylphenyl.
[0015] In the above synthesis method, R2PCF2H(5) and cuprous iodide are used as raw materials, tetrahydrofuran is used as solvent, and the reaction is carried out at 100°C in an air atmosphere for 12 hours.
[0016] The application of copper clusters in the Sonogashira reaction, with the following product structural formula:
[0017]
[0018] The catalytic synthesis method of the endoyne compound is characterized by using terminal alkyne compound 6 (0.5 mmol) and aryl iodine compound 7 (0.5 mmol) as raw materials, palladium acetate (1-3 mol%) as catalyst, copper cluster compounds 1-4 (0.1-1.0 mol%) as copper catalyst, and 2.0-5.0 equivalents of triethylamine as base, reacting at room temperature in an air atmosphere for 1-20 minutes to obtain endoyne compounds 8aa-8aw,8ba-8bu, with a yield of 76-99%. Attached Figure Description
[0019] Figure 1 This is a chemical diagram of the reaction of the present invention. Detailed Implementation
[0020] To make the above-described features, advantages, and objectives of the present invention more apparent, the present invention will be described in detail below with reference to specific embodiments. Many specific details have been set forth in the above description to provide a thorough understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
[0021] Unless otherwise specified, the reaction raw materials and catalysts involved in the following examples are all commercially available reagents.
[0022] Examples of copper cluster preparation 1-4
[0023] Example 1
[0024] 0.2 mmol of R₂PCF₂H (R = phenyl), 0.2 mmol of cuprous iodide, and 1.0 mL of THF were added to a 10 mL reaction tube, and the reaction was stirred overnight at 100 °C. After the reaction was completed, colorless crystals 1 were obtained by recrystallization, with a yield of 95%.
[0025] The NMR data are as follows: 1 H NMR (400MHz, CDCl3) δ7.76(t,J=8.4Hz,4H),7.46(t,J=7.2Hz,2H),7.37(t,J=7.1Hz,4H),6.64(td,J=50.2,28.0Hz,1H).
[0026] The structure of copper cluster compound I is characterized as follows:
[0027]
[0028]
[0029]
[0030] Example 2
[0031] 0.2 mmol of R₂PCF₂H (R = 4-methylphenyl), 0.2 mmol of cuprous iodide, and 1.0 mL of THF were added to a 10 mL reaction tube, and the reaction was stirred overnight at 100 °C. After the reaction was completed, colorless crystals 2 were obtained by recrystallization, with a yield of 98%.
[0032] Example 3
[0033] 0.2 mmol of R₂PCF₂H (R = naphthylphenyl), 0.2 mmol of cuprous iodide, and 1.0 mL of THF were added to a 10 mL reaction tube, and the reaction was stirred overnight at 100 °C. After the reaction was completed, recrystallization yielded colorless crystals 3, with a yield of 86%.
[0034] Example 4
[0035] 0.2 mmol of R2PCF2H (R = 3,5-dimethylphenyl), 0.2 mmol of cuprous iodide, and 1.0 mL of THF were added to a 10 mL reaction tube, and the reaction was stirred overnight at 100 °C. After the reaction was completed, recrystallization yielded colorless crystals 4, with a yield of 88%. Examples 1-44: Preparation of Endoyne Compounds
[0036] Example 1
[0037] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8aa was obtained by column chromatography as a white solid with a yield of 96%.
[0038] The structure of the endoyne compound 8aa is characterized as follows:
[0039] 1 H NMR (400MHz, CDCl3) δ7.51(dd,J=7.2,1.2Hz,2H),7.42(d,J=7.9Hz,2H),7.34–7.27(m,3H),7.12(d,J=7.9Hz,2H),2.33(s,3H). 13 C NMR (101MHz, CDCl3) δ138.3,131.5,131.4,129.1,128.3,128.0,123.4,120.2,89.6,88.7,21.4.
[0040] Example 2
[0041] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8ab was obtained by column chromatography as a white solid with a yield of 98%.
[0042] Example 3
[0043] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8ac was obtained by column chromatography as a yellow solid with a yield of 96%.
[0044] Example 4
[0045] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8ad was obtained by column chromatography as a white solid with a yield of 91%.
[0046] Example 5
[0047] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8ae was obtained by column chromatography as a yellow solid with a yield of 90%.
[0048] Example 6
[0049] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8af was obtained by column chromatography as a yellow solid with a yield of 84%.
[0050] Example 7
[0051] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the endalkyne compound 8 ag was obtained by column chromatography as a yellow solid, with a yield of 89%.
[0052] Example 8
[0053] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8ah was obtained by column chromatography as a colorless solid with a yield of 95%.
[0054] Example 9
[0055] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8ai was obtained by column chromatography as a yellow solid with a yield of 95%.
[0056] Example 10
[0057] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8aj was obtained by column chromatography as a yellow solid with a yield of 92%.
[0058] Example 11
[0059] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the endalkyne compound 8ak was obtained by column chromatography as a colorless oily liquid with a yield of 95%.
[0060] Example 12
[0061] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8al was obtained by column chromatography as a brown solid with a yield of 98%.
[0062] Example 13
[0063] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the endalkyne compound 8am was obtained by column chromatography as a yellow oily liquid with a yield of 97%.
[0064] Example 14
[0065] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8an was obtained by column chromatography as a colorless solid with a yield of 97%.
[0066] Example 15
[0067] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8ao was obtained by column chromatography as a colorless solid with a yield of 98%.
[0068] Example 16
[0069] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the endalkyne compound 8ap was obtained by column chromatography as a brown oily liquid with a yield of 99%.
[0070] Example 17
[0071] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8aq was obtained by column chromatography as a colorless oily liquid with a yield of 97%.
[0072] Example 18
[0073] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8ar was obtained by column chromatography as a colorless oily liquid with a yield of 99%.
[0074] Example 19
[0075] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8as was obtained by column chromatography as a white solid with a yield of 98%.
[0076] Example 20
[0077] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8at was obtained by column chromatography as a white solid with a yield of 76%.
[0078] Example 21
[0079] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8au was obtained by column chromatography as a white solid with a yield of 98%.
[0080] Example 22
[0081] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the endalkyne compound 8av was obtained by column chromatography as a yellow solid with a yield of 96%.
[0082] Example 23
[0083] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8aw was obtained by column chromatography as a white solid with a yield of 91%.
[0084] Example 24
[0085] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8ba was obtained by column chromatography as a white solid with a yield of 98%.
[0086] Example 25
[0087] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8bb was obtained by column chromatography as a white solid with a yield of 99%.
[0088] Example 26
[0089] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the endalkyne compound 8bc was obtained by column chromatography as a yellow oily liquid with a yield of 76%.
[0090] Example 27
[0091] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8bd was obtained by column chromatography as a colorless oily liquid with a yield of 95%.
[0092] Example 28
[0093] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the endalkyne compound 8be was obtained by column chromatography as a yellow oily liquid with a yield of 94%.
[0094] Example 29
[0095] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8bf was obtained by column chromatography as a yellow solid with a yield of 99%.
[0096] Example 30
[0097] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, 8 bg of the endalkyne compound was obtained by column chromatography as a yellow solid, with a yield of 94%.
[0098] Example 31
[0099] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the endalkyne compound 8bh was obtained by column chromatography as a yellow oily liquid with a yield of 93%.
[0100] Example 32
[0101] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8bi was obtained by column chromatography as a white solid with a yield of 82%.
[0102] Example 33
[0103] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8bj was obtained by column chromatography as a yellow solid with a yield of 87%.
[0104] Example 34
[0105] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8bk was obtained by column chromatography as a white solid with a yield of 91%.
[0106] Example 35
[0107] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8b1 was obtained by column chromatography as a colorless oily liquid with a yield of 89%.
[0108] Example 36
[0109] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8bm was obtained by column chromatography as a colorless oily liquid with a yield of 86%.
[0110] Example 37
[0111] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the endalkyne compound 8bn was obtained by column chromatography as a brown oily liquid with a yield of 89%.
[0112] Example 38
[0113] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8bo was obtained by column chromatography as a colorless oily liquid with a yield of 95%.
[0114] Example 39
[0115] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8 bp was obtained by column chromatography as a yellow solid, with a yield of 81%.
[0116] Example 40
[0117] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8bq was obtained by column chromatography as a brown solid with a yield of 76%.
[0118] Example 41
[0119] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature under air for 15 minutes. After the reaction was completed, the internal alkyne compound 8br was obtained by column chromatography as a brown solid with a yield of 84%.
[0120] Example 42
[0121] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the endalkyne compound 8bs was obtained by column chromatography as a brown oily liquid with a yield of 95%.
[0122] Example 43
[0123] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8bt was obtained by column chromatography as a white solid with a yield of 78%.
[0124] Example 44
[0125] In a 10 mL reaction tube, 0.5 mmol of terminal alkyne compound 6, 0.5 mmol of aryl iodine compound 7, 0.01 mmol of palladium acetate, and 0.0025 mmol of copper cluster compound 1 were added. The reaction was carried out at room temperature for 15 minutes under air. After the reaction was completed, the internal alkyne compound 8bu was obtained by column chromatography as a yellow oily liquid with a yield of 87%.
[0126] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be defined by the appended claims.
Claims
1. A novel class of copper cluster compounds, characterized in that... The structural formulas of copper cluster compounds 1, 2, 3, and 4 are as follows: The copper cluster compounds 1, 2, 3 and 4 are synthesized by reacting R2PCF2H with CuI, wherein R is phenyl, 4-methylphenyl, naphthyl or 3,5-dimethylphenyl.
2. A method for synthesizing the novel copper cluster compound according to claim 1, characterized in that, Using R2PCF2H and cuprous iodide as raw materials and tetrahydrofuran as solvent, copper cluster compounds 1, 2, 3 or 4 were obtained after reacting at 100 °C in air for 12 h.
3. An application of the novel copper cluster compound according to claim 1, characterized in that, Copper cluster compound 1 was used in the Sonogashira reaction, and the product structure and yield are as follows: 。 4. The application of the novel copper cluster compound according to claim 3, characterized in that, Using 0.5 mmol of terminal alkyne compound 6 and 0.5 mmol of aryl iodine compound 7 as starting materials, 1-3 mol% palladium acetate as catalyst, 0.1-1.0 mol% copper cluster compound 1 as copper catalyst, and 2.0-5.0 equivalents of triethylamine as base, the reaction was carried out at room temperature in an air atmosphere for 1-20 minutes to give the endalkyne compounds 8aa-8aw, 8ba-8bu, in yields of 76-99%.