Method for synthesizing 1, 1-diaryl compound by using non-activated olefin

Abstract

The invention discloses a method for synthesizing a 1, 1-diaryl compound by using non-activated olefin, and relates to the field of organic synthesis methods and electrochemical catalysis. The invention solves the technical problem that the existing reaction technology is difficult to realize efficient coupling of non-activated olefin and aryl halide to generate the 1, 1-diarylation product. The method comprises the following steps: reducing a nickel catalyst at a cathode through a constant current in an inert gas atmosphere by utilizing an electrochemical means, then carrying out secondary oxidation addition with another aryl halide, and finally carrying out a reduction elimination step to generate the 1, 1-diarylation product. The valence cycle of the nickel catalyst is maintained through an electrochemical condition in the reaction, so that the use of an additional chemical reducing agent is effectively avoided, the operation is simplified, and the environmental burden is reduced. The reaction system disclosed by the invention has high efficiency and universality, can be suitable for various halogenated aromatic hydrocarbons and non-activated olefins under mild conditions, and particularly shows remarkable application value in modification and synthesis of natural products and drug molecules.

Description

Technical Field

[0001] The invention relates to the field of organic synthesis methods and electrochemical catalysis, and in particular to a method for 1,1-diarylation of non-activated olefins. Background Art

[0002] Unactivated olefins are important building blocks in organic synthesis and play a key role in the fields of fine chemicals, pharmaceuticals and functional materials, especially in drug systems containing 1,1-diaryl structures. 1,1-diaryl structures play a key role in their biological activity. For example, the antihistamine chlorpheniramine is often used to relieve allergic symptoms such as rhinitis and urticaria.

[0003] 1,1-Diarylation is an important method for synthesizing polysubstituted aromatic compounds and is widely used in the research and development of drugs, natural products and functional materials. However, existing research has mostly focused on 1,2-diarylation, while research on the 1,1-diarylation of non-activated alkenes is relatively rare. Generally, the 1,1-diarylation reaction of alkenes is challenging due to its difficulty in controlling selectivity and harsh reaction conditions. In addition, traditional methods usually require the use of highly active metal reagents or strong oxidants, which limits the environmental friendliness and ease of operation of the reaction. Therefore, it is of great significance to develop a green, efficient and easy-to-operate method for the 1,1-diarylation of non-activated alkenes. Summary of the invention

[0004] The invention solves the technical problem that it is difficult to realize the efficient coupling of non-activated olefins and halogenated aromatics to generate 1,1-bis-arylation products using existing reaction technologies, and provides a 1,1-bis-arylation synthesis method based on electrochemical reduction nickel catalysis.

[0005] The present invention utilizes electrochemical means to reduce the nickel catalyst to low-valent nickel (0) at the cathode by constant current under an inert gas atmosphere. The nickel species first undergoes oxidative addition with aryl halides to form nickel (II) species, and then after addition to non-activated olefins, nickel migration occurs to form an aromatic nickel compound intermediate. Subsequently, reduction occurs again at the cathode to form a nickel (I) species. Subsequently, a secondary oxidative addition is further performed with another aryl halides, and finally a 1,1-diarylated product is generated through a reduction elimination step, and nickel (I) is formed at the same time, and then the catalytic cycle of the nickel catalyst is completed through a valence change. The nickel catalyst maintains its valence cycle through electrochemical conditions during the reaction, effectively avoiding the use of an external chemical reducing agent, simplifying the operation and reducing the environmental burden. In addition, the reaction system of the present invention is highly efficient and universal, and can be applied to a variety of aryl halides and non-activated olefins under mild conditions, especially in the modification and synthesis of natural products and drug molecules, showing significant application value.

[0006] A method for synthesizing 1,1-biaryl compounds using non-activated olefins is specifically carried out according to the following method:

[0007] 1. Place the anode electrode and cathode electrode in the reaction bottle and place them in N 2 In an atmosphere, non-activated olefin compounds, halogenated aromatics, electrolytes, nickel catalysts, ligands and bases are added, and then ultra-dry solvents are added, and the system is sealed;

[0008] The halogenated aromatic hydrocarbon is iodobenzene, methyl 4-iodobenzoate, p-fluoroiodobenzene, p-chloroiodobenzene, 4'-iodoacetophenone, 4-iodoanisole, 4-iodobenzonitrile, 3-iodobenzo[b]thiophene or ketoprofen;

[0009] The electrolyte is tetrabutylammonium bromide;

[0010] The base in step 1 is 2,6-lutidine;

[0011] 2. Pass a constant current through the closed system of step 1 and stir to obtain a crude product;

[0012] 3. The crude product obtained in step 2 is subjected to reduced pressure distillation to remove the solvent, and then separated and purified by thin layer chromatography to obtain the 1,1-bisaryl compound.

[0013] Furthermore, the non-activated olefin compound in step 1 is vinylboronic acid pinacol ester, trimethylvinylsilane, dimethylphenylvinylsilane, vinylcyclohexane, n-pentene, n-hexene, n-heptene, 4-phenyl-1-butene or keto-ibuprofen butene ester.

[0014] Furthermore, the ultra-dry solvent in step 1 is ultra-dry N,N-dimethylacetamide.

[0015] Furthermore, the nickel catalyst in step 1 is ethylene glycol dimethyl ether nickel bromide.

[0016] Furthermore, the ligand in step 1 is 6,6-dimethyl-2,2-bipyridine.

[0017] Furthermore, in step 1, the ratio of the halogenated aromatic hydrocarbon to the ultra-dry solvent is 0.2mmol:3mL; the ratio of the non-activated olefin compound to the ultra-dry solvent is 0.3-0.4mmol:3mL; the ratio of the nickel catalyst to the ultra-dry solvent is 0.015mmol:3mL; the ratio of the ligand to the ultra-dry solvent is 0.018mmol:3mL; the ratio of the electrolyte to the ultra-dry solvent is 0.3mmol:3mL; and the ratio of the base to the ultra-dry solvent is 0.1mmol:3mL.

[0018] Furthermore, in step 1, the anode electrode is an iron electrode, and the cathode electrode is a nickel electrode.

[0019] Furthermore, in step 2, the current of the constant current is controlled to be 1 mA, the reaction temperature is 30-50° C., and the continuous power-on time is 10 hours.

[0020] Furthermore, in step 2, TLC was used to monitor the progress of the reaction.

[0021] Furthermore, the solvent used for the thin layer chromatography separation and purification in step 3 is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of (5-50):1.

[0022] The general reaction formula of the present invention is as follows:

[0023]

[0024] Wherein R is boric acid pinacol ester, silane or alkyl.

[0025] The reaction mechanism of the present invention is shown in FIG. Figure 3 shown.

[0026] Initially, the nickel complex is electrochemically reduced to generate Ni 0 Species (A). This species undergoes oxidative addition with aryl halide (1) to form aryl nickel intermediate (B). Subsequently, non-activated olefin (2) inserts into the aryl nickel bond to generate intermediate (C). Intermediate (C) then undergoes rapid β-hydrogen elimination and migration insertion steps to generate π-benzyl Ni II Species (D). The π-benzyl intermediate (D) is further reduced at the cathode to generate Ni I Species (E) undergoes oxidative addition with another molecule of aryl halide to generate intermediate (F). Finally, intermediate (F) releases the target 1,1-bisarylation product (3) through reductive elimination and generates Ni I The catalytic cycle involves the addition of Ni I Species (G) is further reduced back to NiO species (A) to complete.

[0027] Beneficial effects of the present invention:

[0028] Compared with the prior art, the present invention synthesizes 1,1-biaryl compounds by a simple, green and efficient method, which has the following advantages:

[0029] (1) The electrons provided by the current in this reaction system serve as cheap and clean reducing agents, avoiding the use of external reducing agents. The reaction operation is simple and the conditions are mild.

[0030] (2) The non-activated olefin compounds, halogenated aromatic compounds, nickel catalysts, nitrogen ligands, bases and ultra-dry solvents used in the reaction system are all simple, cheap and readily available commercial compounds. The iron and nickel electrodes used are also relatively cheap electrode sheets, making the reaction system simple and economical.

[0031] (3) The reaction system has a wide range of substrate applications and can be used to synthesize a variety of 1,1-biaryl compounds. The reaction substrates include various types of polysubstituted halogenated aromatic compounds, non-activated olefin compounds, small molecule olefin compounds, and natural products and drug molecule derivatives.

[0032] (4) The 1,1-biaryl compounds synthesized by the present invention are used in the medical field and can be used as key intermediates or active pharmaceutical ingredients to assist in the development of new drugs and improve therapeutic effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The 1,1-biaryl compound (3-1) obtained in Example 1 1 H NMR spectrum;

[0034] Figure 2 The 1,1-biaryl compound (3-1) obtained in Example 1 13 C NMR spectrum;

[0035] Figure 3 The reaction mechanism diagram of the present invention. DETAILED DESCRIPTION

[0036] Specific implementation method 1: This implementation method is a method for synthesizing 1,1-bisaryl compounds using non-activated olefins, which is specifically carried out according to the following method:

[0037] 1. Place the anode electrode and cathode electrode in the reaction bottle and place them in N 2 In an atmosphere, non-activated olefin compounds, halogenated aromatics, electrolytes, nickel catalysts, ligands and bases are added, and then ultra-dry solvents are added, and the system is sealed;

[0038] The halogenated aromatic hydrocarbon is iodobenzene, methyl 4-iodobenzoate, p-fluoroiodobenzene, p-chloroiodobenzene, 4'-iodoacetophenone, 4-iodoanisole, 4-iodobenzonitrile, 3-iodobenzo[b]thiophene or ketoprofen;

[0039] The electrolyte is tetrabutylammonium bromide;

[0040] The base in step 1 is 2,6-lutidine;

[0041] 2. Pass a constant current through the closed system of step 1 and stir to obtain a crude product;

[0042] 3. The crude product obtained in step 2 is subjected to reduced pressure distillation to remove the solvent, and then separated and purified by thin layer chromatography to obtain the 1,1-bisaryl compound.

[0043] Specific embodiment 2: This embodiment is different from specific embodiment 1 in that: the non-activated olefin compound in step 1 is vinylboronic acid pinacol ester, trimethylvinylsilane, dimethylphenylvinylsilane, vinylcyclohexane, n-pentene, n-hexene, n-heptene, 4-phenyl-1-butene or keto-ibuprofen butene ester. The rest is the same as specific embodiment 1.

[0044] Specific implementation method 3: This implementation method is different from specific implementation method 1 or 2 in that the ultra-dry solvent in step 1 is ultra-dry N,N-dimethylacetamide. The rest is the same as specific implementation method 1 or 2.

[0045] Specific embodiment 4: This embodiment differs from Specific embodiments 1 to 3 in that the nickel catalyst in step 1 is ethylene glycol dimethyl ether nickel bromide. The rest is the same as Specific embodiments 1 to 3.

[0046] Specific embodiment 5: This embodiment differs from specific embodiments 1 to 4 in that the ligand in step 1 is 6,6-dimethyl-2,2-bipyridine. The rest is the same as specific embodiments 1 to 4.

[0047] Specific implementation six: This implementation is different from specific implementations one to five in that: in step one, the ratio of the halogenated aromatic hydrocarbon to the ultra-dry solvent is 0.2mmol:3mL; the ratio of the non-activated olefin compound to the ultra-dry solvent is 0.3-0.4mmol:3mL; the ratio of the nickel catalyst to the ultra-dry solvent is 0.015mmol:3mL; the ratio of the ligand to the ultra-dry solvent is 0.018mmol:3mL; the ratio of the electrolyte to the ultra-dry solvent is 0.3mmol:3mL; the ratio of the base to the ultra-dry solvent is 0.1mmol:3mL. Others are the same as specific implementations one to five.

[0048] Specific implementation example 7: This implementation example is different from specific implementation examples 1 to 6 in that the anode electrode in step 1 is an iron electrode and the cathode electrode is a nickel electrode. The rest is the same as specific implementation examples 1 to 6.

[0049] Specific embodiment 8: This embodiment differs from specific embodiments 1 to 7 in that: in step 2, the current for controlling the constant current is 1 mA, the reaction temperature is 30-50° C., and the continuous power-on time is 10 hours. The rest is the same as specific embodiments 1 to 7.

[0050] Specific embodiment 9: This embodiment differs from specific embodiments 1 to 8 in that: TLC is used to monitor the progress of the reaction in step 2. The rest is the same as specific embodiments 1 to 8.

[0051] Specific embodiment 10: This embodiment differs from specific embodiments 1 to 9 in that the solvent used for separation and purification by thin layer chromatography in step 3 is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of (5-50):1. The rest is the same as specific embodiments 1 to 9.

[0052] The content of the present invention is not limited to the content of the above-mentioned embodiments. The combination of one or several specific embodiments can also achieve the purpose of the invention.

[0053] Embodiment 1:

[0054] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0055] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, an iron anode and a nickel cathode), add 0.2 mmol iodobenzene, 0.3 mmol vinylboronic acid pinacol ester, 0.3 mmol nBu 4 NBr, 0.015mmol NiBr 2 DME, 0.018 mmol 6,6-dimethyl-2,2-bipyridine and 0.1 mmol 2,6-lutidine, and 3.0 mL ultra-dry DMA as solvent, inert gas protection and sealed the system;

[0056] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0057] 3. Extract the crude product obtained in step 2, dry it, remove the solvent by distillation under reduced pressure, and then separate and purify it by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-1) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and its structural formula is:

[0058]

[0059] Purity 99%, yield 77%; its NMR data analysis is: 1 H NMR (400 MHz, CDCl 3 )δ7.29-7.21(m,10H),7.16-7.10(m,2H),4.28(t,J=8.5Hz,1H),1.60(d,J=8.5Hz,2H),1.05(s,12H).

[0060] 13 C NMR (101 MHz, CDCl 3 )δ146.64,128.30,127.74,125.97,83.19,46.58,24.63.

[0061] Embodiment 2:

[0062] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0063] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, an iron anode and a nickel cathode), add 0.2 mmol methyl 4-iodobenzoate, 0.3 mmol vinylboronic acid pinacol ester, 0.3 mmol nBu 4 NBr, 0.015mmol NiBr 2 DME, 0.018 mmol 6,6-dimethyl-2,2-bipyridine and 0.1 mmol 2,6-lutidine, and 3.0 mL ultra-dry DMA as solvent, inert gas protection and sealed the system;

[0064] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0065] 3. Extract the crude product obtained in step 2, dry it, remove the solvent by distillation under reduced pressure, and then separate and purify it by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-2) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and its structural formula is:

[0066]

[0067] Purity 99%, yield 71%; its NMR data analysis is: 1 H NMR (400 MHz, CDCl 3 )δ7.93(d,J=8.3Hz,4H),7.31(d,J=8.3Hz,4H),4.39(t,J=8.3Hz,1H),3.88(s,6H),1.61(d,J=8.3Hz,2H),1.06(s,12H).

[0068] 13 C NMR (101 MHz, CDCl 3 )δ167.07,151.10,129.84,128.22,127.78,83.45,52.08,46.58,24.65.

[0069] Embodiment 3:

[0070] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0071] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, an iron anode and a nickel cathode), add 0.2 mmol 3-iodobenzo[b]thiophene, 0.3 mmol vinylboronic acid pinacol ester, 0.3 mmol nBu 4 NBr, 0.015mmol NiBr 2 DME, 0.018 mmol 6,6-dimethyl-2,2-bipyridine and 0.1 mmol 2,6-lutidine, and 3.0 mL ultra-dry DMA as solvent, inert gas protection and sealed the system;

[0072] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0073] 3. The crude product obtained in step 2 is extracted, dried, and the solvent is removed by distillation under reduced pressure, and then separated and purified by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-3) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and has the structural formula:

[0074]

[0075] Purity 99%, yield 41%; its NMR data analysis is: 1 H NMR (400 MHz, CDCl 3 )δ7.85-7.79(m,2H),7.79-7.74(m,2H),7.32-7.27(m,4H),7.15(s,2H),5.00(t,J=8.1Hz,1H),1.77(d,J=8.1Hz,2H),1.05(s,12H).

[0076] 13 C NMR (101 MHz, CDCl 3 )δ140.80,140.39,138.38,124.21,123.87,122.84,122.40,122.12,83.37,34.71,24.63.

[0077] Embodiment 4:

[0078] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0079] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, iron anode and nickel cathode), add 0.2 mmol iodobenzene, 0.3 mmol vinyltrimethylsilane, 0.3 mmol nBu 4 NBr, 0.015mmol NiBr2 DME, 0.018mmol 6,6-dimethyl-2,2-bipyridine, 0.1mmol 2,6-lutidine, and 3.0mL ultra-dry DMA as solvent, inert gas protection and seal the system;

[0080] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0081] 3. Extract the crude product obtained in step 2, dry it, remove the solvent by distillation under reduced pressure, and then separate and purify it by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-4) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and has the structural formula:

[0082]

[0083] Purity 99%, yield 85%; its NMR data analysis is: 1 H NMR (400MHz, CDCl3) δ7.60(d,J=7.4Hz,4H),7.55(d,J=8.0Hz,4H),7.44(t,J=8.1Hz,8 H),7.34(t,J=7.3Hz,2H),4.20(t,J=8.0Hz,1H),1.51(d,J=8.0Hz,2H),-0.09(s,9H).

[0084] 13 C NMR (101 MHz, CDCl 3 )δ146.28,141.09,139.05,128.80,128.06,127.25,127.14,127.09,46.86,24.36,-0.98.

[0085] Embodiment 5:

[0086] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0087] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, an iron anode and a nickel cathode), add 0.2 mmol iodobenzene, 0.3 mmol dimethylphenylvinylsilane, 0.3 mmol nBu 4 NBr, 0.015mmol NiBr 2 DME, 0.018mmol 6,6-dimethyl-2,2-bipyridine and 0.1mmol 2,6-lutidine, and 3.0mL ultra-dry DMA as solvent, inert gas protection and seal the system;

[0088] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0089] 3. Extract the crude product obtained in step 2, dry it, remove the solvent by distillation under reduced pressure, and then separate and purify it by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-5) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and has the structural formula:

[0090]

[0091] Purity 99%, yield 83%; its NMR data analysis is: 1 H NMR (400MHz, CDCl3) δ7.56-7.51(m,4H),7.48-7.44(m,4H),7.43-7.36(m,6H) ,7.35-7.26(m,9H),4.11(t,J=8.0Hz,1H),1.70(d,J=8.0Hz,2H),0.09(s,6H).

[0092] 13 C NMR (101MHz, CDCl3) δ145.97,141.11,139.16,139.12,133.73,128.95,128.83,128.11,127.86,127.26,127.18,127.12,46.71,23.66,-2.48.

[0093] Embodiment 6:

[0094] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0095] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, an iron anode and a nickel cathode), add 0.2 mmol iodobenzene, 0.4 mmol vinylcyclohexane, 0.3 mmol nBu 4 NBr, 0.015mmol NiBr 2 DME, 0.018 mmol 6,6-dimethyl-2,2-bipyridine and 0.1 mmol 2,6-lutidine, and 3.0 mL ultra-dry DMA were added as solvent.

[0096] Inert gas protection and sealing of the system;

[0097] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0098] 3. Extract the crude product obtained in step 2, dry it, remove the solvent by distillation under reduced pressure, and then separate and purify it by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-6) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and its structural formula is:

[0099]

[0100] Purity 99%, yield 48%; its NMR data analysis is: 1H NMR (400MHz, CDCl3) δ7.61-7.56 (m, 4H), 7.56-7.50 (m, 4H), 7.42 (t, J = 7.7 Hz, 4H), 7.33 (dd, J = 16.1, 7.8 Hz, 6H), 4.16 (t, J = 7.9 Hz, 1H), 2.00 (t, J = 7.3 Hz, 2H), 1.83 (d, J = 12.6 Hz, 2H), 1.75-1.58 (m, 4H), 1.30–1.14 (m, 4H), 1.00 (qd, J = 11.5, 3.3 Hz, 2H).

[0101] 13 C NMR (101 MHz, CDCl 3 )δ201.48,136.61,132.71,128.55,128.53,77.31,49.56,41.07,36.34,36.25,33.72,29.81,29.09.

[0102] Embodiment 7:

[0103] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0104] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, an iron anode and a nickel cathode), add 0.2 mmol iodobenzene, 0.4 mmol n-decene, 0.3 mmol nBu 4 NBr, 0.015mmol NiBr 2 DME, 0.018 mmol 6,6-dimethyl-2,2-bipyridine and 0.1 mmol 2,6-lutidine, and 3.0 mL ultra-dry DMA as solvent, inert gas protection and sealed the system;

[0105] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0106] 3. The crude product obtained in step 2 is extracted, dried, and distilled under reduced pressure to remove the solvent, and then separated and purified by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-7) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and has the structural formula:

[0107]

[0108] Purity 99%, yield 55%; its NMR data analysis is: 1 H NMR (400 MHz, CDCl 3 )δ7.59(d,J=7.7Hz,4H),7.55(d,J=7.8Hz,4H),7.44(t,J=7.5Hz,4H),7.35(dd,J=17.0,7.8Hz,6 H), 4.00 (t, J = 7.8Hz, 1H), 2.13 (q, J = 7.3Hz, 2H), 1.32 (d, J = 36.9Hz, 14H), 0.90 (t, J = 6.6Hz, 3H).

[0109] 13 C NMR (101 MHz, CDCl 3 )δ144.51,141.08,139.05,128.78,128.35,127.26,127.12,127.08,50.86,35.86,31.98,29.76,29.69,29.60,29.40,28.16,22.77,14.20.

[0110] Embodiment 8:

[0111] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0112] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, an iron anode and a nickel cathode), add 0.2 mmol iodobenzene, 0.4 mmol ketobutenol butyl ester (ketobutenol derivative), 0.3 mmol nBu 4 NBr, 0.015mmol NiBr 2 DME, 0.018 mmol 6,6-dimethyl-2,2-bipyridine and 0.1 mmol 2,6-lutidine, and 3.0 mL ultra-dry DMA as solvent, inert gas protection and sealed the system;

[0113] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0114] 3. Extract the crude product obtained in step 2, dry it, remove the solvent by distillation under reduced pressure, and then separate and purify it by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-8) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and has the structural formula:

[0115]

[0116] Purity 99%, yield 45%; its NMR data analysis is: 1 H NMR (400 MHz, CDCl 3 )δ7.60(d,J=7.5Hz,4H),7.55(d,J=8.2Hz,4H),7.45(t,J=7.7Hz,4H),7.35(t,J=7.4Hz,2H),7.30(d ,J=8.3Hz,4H),7.25(d,J=5.3Hz,2H),7.12(d,J=8.1Hz,2H),4.16(tt,J=11.3,5.6Hz,2H),3.96(t,J= 7.9Hz, 1H), 3.73 (q, J = 7.1Hz, 1H), 2.46 (d, J = 7.2Hz, 2H), 2.09 (q, J = 8.2, 7.7Hz, 2H), 1.86 (tq, J = 13. 5,6.6Hz,1H),1.65(dt,J=14.4,6.5Hz,2H),1.53(dd,J=7.1,1.8Hz,3H),0.90(dd,J=6.6,1.8Hz,6H).

[0117] 13 C NMR (101 MHz, CDCl 3 )δ174.90,143.81,143.75,140.99,140.62,139.28,137.97,129.43,128.84,128.29,128.27,1 27.36,127.30,127.22,127.10,64.51,50.29,45.32,45.16,31.89,30.26,27.28,22.50,18.57.

[0118] Embodiment 9:

[0119] This embodiment provides a method for synthesizing 1,1-biaryl compounds using non-activated olefins, which is specifically carried out in the following manner:

[0120] 1. In a dry 8 mL reaction vial (equipped with a magnetic stirrer, iron anode and nickel cathode), add 0.2 mmol iodobenzene, 1 bar ethylene, 0.3 mmol nBu 4 NBr, 0.015mmol NiBr2 DME, 0.018 mmol 6,6-dimethyl-2,2-bipyridine and 0.1 mmol 2,6-lutidine, and 3.0 mL ultra-dry DMA as solvent, inert gas protection and sealed the system;

[0121] 2. Stir the sealed system in step 1 at room temperature, continuously pass a constant current of 1 mA, and react for 10 hours to obtain a crude product;

[0122] 3. Extract the crude product obtained in step 2, dry it, remove the solvent by distillation under reduced pressure, and then separate and purify it by thin layer chromatography to obtain a product, which is identified as a 1,1-diaryl compound (3-9) by nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum, and has the structural formula:

[0123]

[0124] Purity 99%, yield 30%; its NMR data analysis is: 1 H NMR (400 MHz, CDCl 3 )δ7.66(d,J=7.2Hz,4H),7.62(d,J=8.0Hz,4H),7.50(t,J=7.6Hz,4H),7.44-7.38(m,6H),4.32(q,J=7.2Hz,1H),1.80(d,J=7.2Hz,3H).

[0125] 13 C NMR (101 MHz, CDCl 3 )δ145.50,141.09,139.15,128.84,128.15,127.29,127.19,127.14,44.30,22.00.

[0126] The above-described embodiment is only a preferred solution of the present invention and does not limit the present invention in any form. There are other variations and modifications without exceeding the technical solution described in the claims.

Claims

1. A method for synthesizing 1,1-bisaryl compounds using non-activated olefins, characterized in that The method is specifically carried out as follows:

1. Place an anode electrode and a cathode electrode in a reaction bottle, add non-activated olefin compounds, halogenated aromatic hydrocarbons, electrolytes, nickel catalysts, ligands and bases under N2 atmosphere, and then add ultra-dry solvents to seal the system; The halogenated aromatic hydrocarbon is iodobenzene, methyl 4-iodobenzoate, p-fluoroiodobenzene, p-chloroiodobenzene, 4'-iodoacetophenone, 4-iodoanisole, 4-iodobenzonitrile, 3-iodobenzo[b]thiophene or ketoprofen; The electrolyte is tetrabutylammonium bromide; The base in step 1 is 2,6-lutidine; 2. Pass a constant current through the closed system of step 1 and stir to obtain a crude product; 3. The crude product obtained in step 2 is subjected to reduced pressure distillation to remove the solvent, and then separated and purified by thin layer chromatography to obtain the 1,1-bisaryl compound.

2. A method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that In step 1, the non-activated olefin compound is vinylboronic acid pinacol ester, trimethylvinylsilane, dimethylphenylvinylsilane, vinylcyclohexane, n-pentene, n-hexene, n-heptene, 4-phenyl-1-butene or keto-ibuprofen butene ester.

3. A method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that The ultra-dry solvent in step 1 is ultra-dry N,N-dimethylacetamide.

4. A method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that The nickel catalyst in step 1 is ethylene glycol dimethyl ether nickel bromide.

5. A method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that The ligand in step 1 is 6,6-dimethyl-2,2-bipyridine.

6. A method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that In step 1, the dosage ratio of the halogenated aromatic hydrocarbon to the ultra-dry solvent is 0.2mmol:3mL; the dosage ratio of the non-activated olefin compound to the ultra-dry solvent is 0.3-0.4mmol:3mL; the dosage ratio of the nickel catalyst to the ultra-dry solvent is 0.015mmol:3mL; the dosage ratio of the ligand to the ultra-dry solvent is 0.018mmol:3mL; the dosage ratio of the electrolyte to the ultra-dry solvent is 0.3mmol:3mL; and the dosage ratio of the base to the ultra-dry solvent is 0.1mmol:3mL.

7. A method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that In step 1, the anode electrode is an iron electrode, and the cathode electrode is a nickel electrode.

8. The method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that Step 2: The current of the constant current is controlled to be 1 mA, the reaction temperature is 30-50° C., and the continuous power-on time is 10 hours.

9. The method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that In step 2, TLC was used to monitor the reaction progress.

10. The method for synthesizing 1,1-bisaryl compounds using non-activated olefins according to claim 1, characterized in that The solvent used for the thin layer chromatography separation and purification in step 3 is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of (5-50):1.

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