A method for synthesizing aryl phosphine compounds from aryl triflate ethers using nickel catalyst

Abstract

The application develops a method for synthesizing aryl phosphine compounds from aryl trifluoromethoxy ether, specifically, aryl trifluoromethoxy ether (Ar-OCF3) and diphenyl phosphine oxide are coupled under the action of a nickel catalyst, a reducing coupling reagent phenyl silane and a base to prepare aryl phosphine compounds. The method breaks the dependence of traditional C-P bond construction on high-activity reagents, realizes efficient conversion of the inert structural unit Ar-OCF3, and can be applied to industrial preparation.

Description

Technical Field

[0001] This invention relates to the field of organophosphine synthesis technology, and specifically to a method for synthesizing arylphosphine compounds from nickel-catalyzed aryltrifluoromethoxy ethers. Background Technology

[0002] Phosphine-containing compounds have wide applications in synthetic chemistry, medicinal chemistry, agricultural chemistry, and materials chemistry. Based on the type of CP bond in organophosphine compounds, they can be classified into arylphosphine compounds, alkynylphosphine compounds, and alkylphosphine compounds. Among these, arylphosphine compounds, including arylphosphine alkanes, aryl phosphates, phosphacyclopentadienes, and their derivatives, play crucial roles in organic synthesis, polymer flame retardant materials, functional materials, and biochemistry. For example, they act as ligands and catalysts in numerous transition metal and small molecule-catalyzed organic reactions. Triarylphosphine compounds play a significant role in organic synthesis, medicinal chemistry, and materials science. These compounds can be used as organophosphine ligands or catalysts to promote reactions, such as transition metal-catalyzed cross-coupling reactions, asymmetric catalytic reactions, and cycloaddition reactions. They also serve as basic building blocks in reactions such as the Appel reaction, the Mitsunobu reaction, and the Wittig reaction. Furthermore, triarylphosphine compounds can improve the thermal stability of materials in the form of flame suppressants.

[0003] Among alkoxy functional groups, trifluoromethoxy is a fluorinated group with a strong electron-withdrawing effect. As a fluorinated derivative of methoxy, trifluoromethoxy is widely incorporated into bioactive molecules to enhance their chemical properties due to its unique high metabolic stability, electronegativity, and lipophilicity, and it also has wide applications in pesticides, fertilizers, and pharmaceuticals. However, as a fluorinated compound, its low solubility in water and high carbon-fluorine bond dissociation energy result in excellent stability. Long-term presence in the environment can have adverse effects on human health and ecosystems. Trifluoromethoxy aromatics themselves are stable compounds, and their Ar-OCF3 bonds are generally inert. Although the formation of Ar-OCF3 bonds has been extensively studied, methods for activating these bonds have not been fully explored. Therefore, developing efficient methods for synthesizing arylphosphides by functionalizing Ar-OCF3 bonds to construct CP bonds is particularly important.

[0004] In 1997, A. Thiebault's team reported the irreversible stepwise reduction of trifluoromethoxy aromatics in liquid ammonia. The trifluoromethoxy group, acting as a leaving group, first undergoes electron transfer, followed by cleavage by a transient anionic radical, and finally the substrate is reduced to an aromatic hydrocarbon (C. Combellas, F. Kanoufi, A. Thiebault, J. Electroanal. Chem. 1997, 432, 181-192).

[0005] .

[0006] In 2004, John W. Dankwardt's team reported a general, high-yield nickel-catalyzed cross-coupling reaction of inactive aromatic ethers with aryl Grignard reagents (John W. Dankwardt, Angew. Chem. Int. Ed. 2004, 43, 2428-2432). This reaction has a very broad range of aromatic ether derivatives and can synthesize desired biaryl compounds in high yields.

[0007] .

[0008] In 2008, Hideki Amii's team used sodium metal as a reducing agent to synthesize polysubstituted aromatic hydrocarbons with high regioselectivity via the Ar-OCF3 bond cleavage silanization reaction of trifluoromethoxy aromatic hydrocarbons (Akinori Iijima and HidekiAmii, Tetrahedron Letters. 2008, 49, 6013-6015).

[0009] .

[0010] In 2019, Burkhard Konig's team reported the first example of photocatalytic generation of highly electrophilic intermediates not based on radical reactivity (Daniel Petzold, Philipp Nitschke and Burkhard Konig, Chem. Eur. J. 2019, 25, 361-366). 4-(trifluoromethoxy)benzonitrile, after single-electron reduction by an organic photosensitizer, cleaves into fluorophosgene and benzonitrile. The fluorophosgene generated in situ through intramolecular cyclization can be used to prepare carbonates, carbamates, and urea derivatives in moderate to excellent yields.

[0011] .

[0012] In 2025, Jun Hee Lee and Eunsung Lee's team developed a simple and efficient catalytic system for the borylation of aryl trifluoromethoxy compounds (Jongheon Jeong, Jun Hee Lee and Eunsung Lee, Org. Lett. 2025, 27, 22, 5852-5857). This method provides a practical approach for converting long-term OCF3-containing agrochemicals in the environment into valuable arylborides.

[0013] .

[0014] In 2026, Xiao-Feng Wu's team reported a nickel-catalyzed aminocarbonylation reaction of ArOCF3 with amines using inositol hexacarboxylate (HFI) as the CO source (Zhen-Wei Liu, Chang-Sheng Kuai, and Xiao-Feng Wu, Org. Lett. 2026). This reaction exhibits broad compatibility with various aniline derivatives and can adapt to various electronic and steric requirements. This work not only expands the aryl source for amide synthesis from traditional electrophilic reagents to the highly robust ArOCF3 motif, but also provides a blueprint for phenol activation.

[0015] .

[0016] Existing technologies suffer from problems such as limited substrate availability, complex reaction conditions, and low yields. The method provided by this invention overcomes the dependence of traditional CP bond construction on highly active reagents, achieving a high-value transformation of the inert structural unit Ar-OCF3. Summary of the Invention

[0017] To address the shortcomings of existing technologies, this invention develops a method for synthesizing arylphosphine compounds from aryl trifluoromethoxy ethers using nickel catalysis.

[0018] This invention first provides an arylphosphine compound of the formula JPP-3, with the following structural formula:

[0019] ,

[0020] Ar is a monosubstituted phenyl group, with the following structural formula: ;

[0021] When R1 is methyl, L is phenyl;

[0022] When R1 is hydrogen

[0023] L is independently selected from substituted phenyl groups. or ;

[0024] When L is a substituted phenyl group, the substituent on the ring of the substituted phenyl group is one or more, which are methyl, phenyl, pyridine or hydroxyl.

[0025] More preferably, the present invention provides an arylphosphine compound of formula JPP-3, with the following specific structure: .

[0026] This invention further provides a nickel-catalyzed method for synthesizing arylphosphine compounds from aryltrifluoromethoxy ethers. Specifically, the method involves preparing arylphosphine compound JPP-3 from aryltrifluoromethoxy ether compound JPP-1 (Ar-OCF3) and diphenylphosphine oxide compound JPP-2 via a coupling reaction under the action of a nickel catalyst, a reducing coupling agent phenylsilane (PhSiH3), and a base.

[0027] ,

[0028] Ar is a monosubstituted phenyl group, with the following structural formula: ;

[0029] L is independently selected from phenyl, substituted phenyl. , diphenylamine or ;

[0030] When L is a substituted phenyl group, the substituent on the ring of the substituted phenyl group is one or more, and is a C1-C3 alkyl, phenyl, or diphenylamino group. pyridine, hydroxyl or dimethylamino;

[0031] R1 is hydrogen or a C1-C3 alkyl group; when R1 is a C1-C3 alkyl group, L is a phenyl group.

[0032] The group structures defined by compounds of formula JPP-1 and JPP-2 are determined by referring to the specific structure of compound JPP-3 and the above coupling reaction.

[0033] More preferably, the diphenylphosphine oxide compound of formula JPP-2 is selected from the following compounds:

[0034] .

[0035] More preferably, the arylphosphine compound JPP-3 obtained by the coupling reaction is selected from the following compounds:

[0036] .

[0037] The nickel catalyst is nickel bromide with ethylene glycol dimethyl ether.

[0038] The alkali is NaOH (sodium hydroxide), NaOAc (sodium acetate), NaH (sodium hydride), KOH (potassium hydroxide), t-BuOK (potassium tert-butoxide), t-BuOLi (lithium tert-butoxide), or t-BuONa (sodium tert-butoxide); more preferably, the alkali is t-BuOK;

[0039] The molar ratio of the aryltrifluoromethoxy ether compound JPP-1, the diphenylphosphine oxide compound JPP-2, the base, and the reducing coupling agent is 1:3:3:4;

[0040] The reaction temperature of the coupling reaction is 80-150℃; more preferably, the reaction temperature of the coupling reaction is 130℃.

[0041] The reaction time of the coupling reaction is 16-32 hours; more preferably, the reaction time of the coupling reaction is 24 hours.

[0042] The coupling reaction requires the addition of solvent DMA (N,N-dimethylacetamide) to the reaction system, followed by the slow addition of a small amount of DMA-diluted reducing coupling agent PhSiH3 to the system.

[0043] This invention develops a one-step method for the efficient synthesis of a series of valuable arylphosphine compounds using aryltrifluoromethoxy ether (Ar-OCF3) as the aryl source, under the synergistic effect of a nickel catalyst, a phenylsilane reductive coupling agent, and a base. This method achieves the breaking of the inert C(sp2)-OCF3 bond and the construction of the CP bond. This invention overcomes the problems of limited substrate availability, complex reaction conditions, and low yields in existing technologies, and breaks through the dependence of traditional CP bond construction on highly reactive reagents. It realizes the high-value transformation of the inert structural unit Ar-OCF3, which can be widely used in the preparation of organophosphine ligands, pharmaceutical intermediates, and functional materials, possessing extremely high industrial application value and environmental benefits. Detailed Implementation

[0044] To further understand the present invention, the following detailed description is provided in conjunction with embodiments. It should be understood that these embodiments are merely for further detailing the features of the method for synthesizing arylphosphine compounds from nickel-catalyzed aryl trifluoromethoxy ethers according to the present invention, and are not intended to limit the scope of the present invention or the scope of the claims.

[0045] The specific structures of compounds JPP-1 and JPP-2 involved in the examples can be determined based on the structures of products JPP-3a to JPP-3x and the following coupling reactions:

[0046] ,

[0047] Ar is a monosubstituted phenyl group, with the following structural formula: ;

[0048] L is independently selected from phenyl, substituted phenyl. , diphenylamine or ;

[0049] When L is a substituted phenyl group, the substituent on the ring of the substituted phenyl group is one or more, and is a C1-C3 alkyl, phenyl, or diphenylamino group. pyridine, hydroxyl or dimethylamino;

[0050] R1 is hydrogen or a C1-C3 alkyl group; when R1 is a C1-C3 alkyl group, L is a phenyl group.

[0051] Example 1:

[0052]

[0053] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1a (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130 °C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3a (437 mg), a white solid with a yield of 86%. During this process, the target product was easily oxidized. The product was dissolved in deuterated chloroform (CDCl3) and its structure was characterized by NMR. 1 HNMR (400 MHz, CDCl3) δ 7.64 – 7.57 (m, 4H), 7.49 – 7.34 (m, 15H). 31 P NMR (162MHz, CDCl3) δ -6.08. 13 C NMR (100 MHz, CDCl3) δ 141.61, 140.64, 137.28 (d, J C-P= 10.6 Hz), 136.19 (d, J C-P = 10.7 Hz), 134.31 (d, J C-P = 19.5 Hz), 133.90 (d,J C-P = 19.5 Hz), 128.96, 128.91, 128.68 (d, J C-P = 7.0 Hz), 127.68, 127.31 (d,J C-P = 7.0 Hz), 127.21.

[0054] Example 2:

[0055]

[0056] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1b (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add DMA solvent (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3b (428 mg), a white solid with a yield of 81%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.57 (d, J = 7.7 Hz, 2H), 7.51 (d, J = 7.9 Hz, 2H), 7.43 – 7.33(m, 12H), 7.28 – 7.24 (m, 2H), 2.41 (s, 3H). 31 P NMR (162 MHz, CDCl3) δ -6.07. 13C NMR (100 MHz, CDCl3) δ 141.59, 137.75, 137.53, 137.32 (d, J C-P = 10.2Hz), 135.70 (d, J C-P = 10.4 Hz), 134.32 (d, J C-P = 19.5 Hz), 133.89 (d, J C-P =19.5 Hz), 129.69, 128.89, 128.67 (d, J C-P = 6.9 Hz), 127.11 (d, J C-P = 7.2 Hz), 127.04, 21.26.

[0057] Example 3:

[0058]

[0059] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1c (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3c (528 mg), a white solid with a yield of 96%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.59 – 7.55 (m, 2H), 7.42 – 7.34 (m, 12H), 7.23 (s, 2H), 7.02(s, 1H), 2.39 (s, 6H). 31P NMR (162 MHz, CDCl3) δ -6.10. 13 C NMR (100 MHz, CDCl3)δ 141.94, 140.68, 138.45, 137.31 (d, J C-P = 10.4 Hz), 135.78 (d, J C-P = 10.1Hz), 134.23 (d, J C-P = 19.5 Hz), 133.89 (d, J C-P = 19.4 Hz), 129.33, 128.88,128.66 (d, J C-P = 7.0 Hz), 127.36 (d, J C-P = 7.1 Hz), 125.17, 21.54.

[0060] Example 4:

[0061]

[0062] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1d (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3d (542 mg), a white solid with a yield of 93%. The target product was readily oxidized during this process. The product was dissolved in CDCl3, and its structure was characterized by NMR. 11H NMR (400MHz, CDCl3) δ 8.07 (d, J = 1.8 Hz, 1H), 7.95 – 7.86 (m, 3H), 7.78 – 7.70 (m,3H), 7.54 – 7.48 (m, 2H), 7.45 (t, J = 7.8 Hz, 2H), 7.43 – 7.36 (m, 10H). 31 31P NMR (162 MHz, CDCl3) δ -6.04. 13 13C NMR (100 MHz, CDCl3) δ 141.52, 137.97, 137.26(d, J C-P = 10.6 Hz), 136.32 (d, J C-P = 10.8 Hz), 134.40 (d, J C-P = 19.5 Hz),133.92 (d, J C-P = 19.6 Hz), 133.78, 132.88, 128.94, 128.71 (d, J C-P = 6.9 Hz),128.66, 128.37, 127.79, 127.57 (d, J C-P = 7.0 Hz), 126.50, 126.22, 126.01,125.48.

[0063] Example 5:

[0064]

[0065] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1e (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3e (497 mg), a white solid with a yield of 80%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.70 (s, 4H), 7.68 (d, J = 1.6 Hz, 1H), 7.65 (d, J = 1.3 Hz, 2H), 7.63 (d, J = 1.5 Hz, 1H), 7.51 – 7.43 (m, 3H), 7.43 – 7.36 (m, 12H). 31 PNMR (162 MHz, CDCl3) δ -6.01. 13 C NMR (100 MHz, CDCl3) δ 141.07, 140.71,140.52, 139.51, 137.28 (d, J C-P = 10.8 Hz), 136.33 (d, J C-P = 10.8 Hz), 134.45,134.26, 134.01, 133.82, 128.97, 128.93, 128.69 (d, J C-P = 6.9 Hz), 127.68,127.55, 127.17 (d, J C-P = 7.0 Hz), 127.16.

[0066] Example 6:

[0067]

[0068] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1f (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add DMA solvent (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3f (496 mg), a white solid with a yield of 90%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.42 – 7.36 (m, 12H), 7.35 (t, J = 2.2 Hz, 1H), 7.33 – 7.30 (m,2H), 7.29 – 7.26 (m, 2H), 7.26 – 7.25 (m, 1H), 2.30 (s, 3H). 31 P NMR (162 MHz, CDCl3) δ -5.84. 13 C NMR (100 MHz, CDCl3) δ 142.52, 141.46, 137.27 (d, J C-P =10.3 Hz), 135.46 (d, J C-P = 10.2 Hz), 135.45, 133.95 (d, J C-P = 19.5 Hz), 133.54 (d, J C-P = 19.5 Hz), 130.53, 129.87, 129.48 (d, J C-P = 7.0 Hz), 128.93,128.68 (d, J C-P= 7.1 Hz), 127.56, 125.96, 20.65.

[0069] Example 7:

[0070]

[0071] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1 g (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130 °C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3g (438mg) as a white solid, with a yield of 75%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 8.92 (dd, J = 4.3, 1.7 Hz, 1H), 8.23 ​​– 8.16 (m, 2H), 8.02 –7.95 (m, 2H), 7.72 – 7.67 (m, 2H), 7.47 – 7.36 (m, 13H). 31 P NMR (162 MHz, CDCl3) δ -6.07. 13 C NMR (100 MHz, CDCl3) δ 150.49, 147.74, 140.57, 138.78,137.09 (d, J C-P = 10.8 Hz), 137.05 (d, J C-P = 11.5 Hz), 136.50, 134.41 (d, J C-P = 19.4 Hz), 133.90 (d, J C-P= 19.5 Hz), 130.02, 129.17, 128.97, 128.70 (d, J C-P = 7.0 Hz), 128.57, 127.56 (d, J C-P = 6.9 Hz), 125.66, 121.65.

[0072] Example 8:

[0073]

[0074] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1h (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3h (625 mg), a white solid with a yield of 97%. The target product was readily oxidized during this process. The product was dissolved in CDCl3, and its structure was characterized by NMR. 1 H NMR (400MHz, CDCl3) δ 7.37 – 7.29 (m, 10H), 7.28 – 7.22 (m, 4H), 7.19 – 7.14 (m, 2H), 7.14 – 7.09 (m, 4H), 7.06 – 6.98 (m, 4H). 31 P NMR (162 MHz, CDCl3) δ -6.60. 13 CNMR (100 MHz, CDCl3) δ 148.68, 147.39, 137.82, 137.72, 135.00 (d, J C-P = 20.8Hz), 133.69 (d, J C-P= 19.2 Hz), 129.48, 128.70, 128.57 (d, J C-P = 6.9 Hz),125.19, 123.61, 122.33 (d, J C-P = 7.8 Hz).

[0075] Example 9:

[0076]

[0077] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1i (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130 °C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3i (667 mg), a white solid with a yield of 88%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.55 (d, J = 6.7 Hz, 2H), 7.47 (d, J = 8.5 Hz, 2H), 7.36 (d, J= 3.8 Hz, 12H), 7.29 – 7.25 (m, 4H), 7.16 – 7.10 (m, 6H), 7.04 (t, J = 7.3Hz, 2H). 31 P NMR (162 MHz, CDCl3) δ -6.25. 13 C NMR (100 MHz, CDCl3) δ 147.72,147.64, 141.16, 134.35 (d, J C-P = 19.3 Hz), 133.89 (d, JC-P = 19.4 Hz), 129.45,128.95, 128.69 (d, J C-P = 7.0 Hz), 127.83, 126.78 (d, J C-P = 7.1 Hz), 124.69, 123.81, 123.21.

[0078] Example 10:

[0079]

[0080] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1j (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3j (710 mg), a white solid with a yield of 94%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 8.18 (d, J = 7.7 Hz, 2H), 7.86 – 7.80 (m, 2H), 7.67 (td, J =8.4, 1.7 Hz, 4H), 7.52 – 7.37 (m, 16H), 7.35 – 7.30 (m, 2H). 31 P NMR (162 MHz, CDCl3) δ -6.09. 13 C NMR (100 MHz, CDCl3) δ 140.90, 140.60, 139.64, 137.24,137.11 (d, J C-P= 10.4 Hz), 136.75 (d, J C-P = 11.1 Hz), 134.43 (d, J C-P = 19.5Hz), 133.94 (d, J C-P = 19.5 Hz), 129.01, 128.74 (d, J C-P = 7.0 Hz), 128.56,127.48, 127.27 (d, J C-P = 7.0 Hz), 126.11, 123.57, 120.47, 120.16, 109.95.

[0081] Example 11:

[0082]

[0083] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1k (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3k (689 mg), a white solid with a yield of 94%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 8.85 (s, 1H), 8.75 – 8.62 (m, 5H), 7.88 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 7.7 Hz, 2H), 7.71 – 7.63 (m, 4H), 7.49 (t, J = 7.6 Hz, 2H), 7.46– 7.35 (m, 10H).31 P NMR (162 MHz, CDCl3) δ -6.00. 13 C NMR (100 MHz, CDCl3) δ141.56, 139.25, 137.25 (d, J C-P = 10.5 Hz), 136.55 (d, J C-P = 10.8 Hz), 134.49(d, J C-P = 19.5 Hz), 133.94 (d, J C-P = 19.5 Hz), 130.23, 130.17, 129.96,129.86, 129.67, 129.26, 128.98, 128.74 (d, J C-P = 7.0 Hz), 127.59, 127.49 (d,J C-P = 7.4 Hz), 127.40, 126.29, 124.10, 123.49 (d, J C-P = 1.6 Hz), 123.48 (d,J C-P = 10.7 Hz), 121.89.

[0084] Example 12:

[0085]

[0086] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1l (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3l (598 mg), a white solid with a yield of 96%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 8.69 (d, J = 5.2 Hz, 2H), 7.75 – 7.70 (m, 4H), 7.62 (dd, J =7.1, 1.3 Hz, 2H), 7.56 (d, J = 5.1 Hz, 2H), 7.45 – 7.34 (m, 12H). 31 P NMR (162MHz, CDCl3) δ -6.10. 13 C NMR (100 MHz, CDCl3) δ 150.35, 147.85, 141.37, 140.48,137.22, 137.10 (d, J C-P = 10.4 Hz), 137.00 (d, J C-P = 10.7 Hz), 134.36 (d, J C-P = 19.5 Hz), 133.89 (d, J C-P = 19.6 Hz), 128.96, 128.69 (d, J C-P = 7.1 Hz),127.86, 127.55, 127.18 (d, J C-P = 6.9 Hz), 121.56.

[0087] Example 13:

[0088]

[0089] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1m (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add DMA solvent (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3m (324 mg), a white solid, with a yield of 61%. During this process, the target product was readily oxidized and treated with deuterated dimethyl sulfoxide (DMSO-). d 6) The structure of the dissolution products was characterized by NMR: 1 H NMR (400 MHz, DMSO-d6) δ 9.62 (s, 1H), 7.62 (d, J = 7.9 Hz, 2H), 7.51(d, J = 8.2 Hz, 2H), 7.46 – 7.35 (m, 6H), 7.34 – 7.19 (m, 6H), 6.86 (d, J =8.2 Hz, 2H). 31 P NMR (162 MHz, DMSO-d6) δ -7.63. 13 C NMR (100 MHz, DMSO-d6) δ157.46, 140.73, 136.79 (d, J C-P = 11.4 Hz), 134.12 (d, J C-P = 10.8 Hz), 133.83(d, J C-P = 19.8 Hz), 133.21 (d, J C-P= 19.4 Hz), 130.01, 128.93, 128.76 (d, J C-P = 6.9 Hz), 127.80, 126.20 (d, J C-P = 7.0 Hz), 115.78.

[0090] Example 14:

[0091]

[0092] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1n (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3n (544 mg), a white solid with a yield of 95%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.55 (t, J = 9.4 Hz, 4H), 7.44 – 7.30 (m, 12H), 6.82 (d, J =8.4 Hz, 2H), 3.01 (s, 6H). 31 P NMR (162 MHz, CDCl3) δ -6.15. 13 C NMR (100 MHz, CDCl3) δ 150.23, 141.69, 137.64 (d, J C-P = 10.8 Hz), 134.49, 134.28 (d, J C-P =2.2 Hz), 134.19, 133.95 (d, J C-P= 1.9 Hz), 133.75 (d, J C-P = 1.9 Hz), 128.77(d, J C-P = 2.1 Hz), 128.66 (d, J C-P = 2.2 Hz), 128.59 (d, J C-P = 2.2 Hz),127.80, 126.45, 126.39, 126.32, 112.88, 40.68.

[0093] Example 15:

[0094]

[0095] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1o (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3o (355 mg), a white solid with a yield of 61%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.99 (s, 1H), 7.92 – 7.84 (m, 3H), 7.75 (dd, J = 16.6, 8.2 Hz, 2H), 7.68 (dd, J = 8.5, 1.9 Hz, 1H), 7.54 – 7.36 (m, 13H), 7.31 (t, J = 7.2Hz, 1H). 31 P NMR (162 MHz, CDCl3) δ -4.94. 13C NMR (100 MHz, CDCl3) δ 141.27 (d,J C-P = 7.8 Hz), 138.15, 138.04, 137.22 (d, J C-P = 10.8 Hz), 133.91 (d, J C-P =19.5 Hz), 133.71, 133.14, 132.90, 132.76, 132.65 (d, J C-P = 15.9 Hz), 129.15(d, J C-P = 6.2 Hz), 128.95, 128.70 (d, J C-P = 6.8 Hz), 128.58, 128.32, 127.94,127.74, 126.45, 126.07 (d, J C-P = 16.7 Hz), 125.54.

[0096] Example 16:

[0097]

[0098] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1p (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3p (492 mg), a white solid with a yield of 97%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1H NMR (400MHz, CDCl3) δ 7.61 (tt, J = 9.2, J =1.6, 1.8 Hz, 2H), 7.55 – 7.51 (m, 2H),7.46 – 7.26 (m, 15H). 31 P NMR (162 MHz, CDCl3) δ −5.04. 13 C NMR (100 MHz, CDCl3)δ 141.37 (d, J C-P = 7.5 Hz), 140.85, 137.88 (d, J C-P = 10.8 Hz), 137.11 (d, J C-P = 10.4 Hz), 133.90 (d, J C-P = 19.4 Hz), 132.75 (d, J C-P = 8.4 Hz), 132.55 (d,J C-P = 3.2 Hz), 129.05 (d, J C-P = 6.5 Hz), 128.95, 128.91, 128.68 (d, J C-P = 7.0Hz), 127.72, 127.55, 127.25。

[0099] Chapter 17:

[0100]

[0101] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1q (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3q (489 mg), a white solid with a yield of 89%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.64 (dt, J = 8.8, 1.7 Hz, 1H), 7.58 (dt, J = 7.7, 1.4 Hz, 1H), 7.44 – 7.35 (m, 11H), 7.24 (t, J = 7.5 Hz, 1H), 7.16 (s, 2H), 7.00 (s, 1H), 2.37 (s, 6H). 31 P NMR (162 MHz, CDCl3) δ -4.96. 13 C NMR (100 MHz, CDCl3) δ 141.59(d, J C-P = 8.0 Hz), 140.86, 138.42, 137.70 (d, J C-P = 11.0 Hz), 137.29 (d, J C-P = 10.8 Hz), 133.89 (d, J C-P = 19.4 Hz), 132.91 (d, J C-P = 24.3 Hz), 132.37 (d,J C-P = 15.4 Hz), 129.18, 128.95 (d, J C-P= 6.0 Hz), 128.87, 128.65 (d, J C-P =6.9 Hz), 127.74, 125.19, 21.50.

[0102] Example 18:

[0103]

[0104] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1r (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130 °C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3r (344 mg), a white solid with a yield of 47%. The target product was readily oxidized during this process. The product was dissolved in CDCl3, and its structure was characterized by NMR. 1 H NMR (400MHz, CDCl3) δ 8.74 (s, 1H), 8.70 – 8.57 (m, 5H), 7.86 – 7.76 (m, 3H), 7.67(q, J = 4.9 Hz, 4H), 7.52 (t, J = 7.6 Hz, 1H), 7.48 – 7.32 (m, 11H). 31 P NMR (162 MHz, CDCl3) δ -5.09. 13 C NMR (100 MHz, CDCl3) δ 141.17 (d, J C-P = 7.3 Hz),139.29, 138.20 (d, J C-P = 11.3 Hz), 137.19 (d, J C-P= 10.5 Hz), 133.97 (d, J C-P = 19.4 Hz), 132.95 (d, J C-P = 22.1 Hz), 132.90 (d, J C-P = 17.3 Hz), 130.14 (d,J C-P = 2.6 Hz), 129.92, 129.72 (d, J C-P = 18.7 Hz), 129.22 (d, J C-P = 6.5 Hz),129.14, 129.01, 128.75 (d, J C-P = 6.9 Hz), 127.80, 127.42 (d, J C-P = 15.6 Hz),127.42, 126.21, 124.03, 123.47, 123.46 (d, J C-P = 4.9 Hz), 121.84.

[0105] Example 19:

[0106]

[0107] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1s (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3s (548 mg), a white solid with a yield of 94%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1H NMR (400MHz, CDCl3) δ 7.84 (d, J = 7.6 Hz, 1H), 7.78 (d, J = 8.4 Hz, 1H), 7.61 (d, J= 7.6 Hz, 1H), 7.56 (s, 1H), 7.49 – 7.39 (m, 5H), 7.37 – 7.25 (m, 11H), 7.18– 7.12 (m, 1H). 31 P NMR (162 MHz, CDCl3) δ -13.66. 13 C NMR (100 MHz, CDCl3) δ148.33 (d, J = 29.0 Hz), 139.30 (d, J C-P = 6.3 Hz), 137.77 (d, J C-P = 11.2 Hz),136.22 (d, J C-P = 13.9 Hz), 134.37, 134.19, 133.99, 132.83, 132.57, 130.48 (d,J C-P = 5.0 Hz), 128.98 (d, J C-P = 4.0 Hz), 128.90, 128.64, 128.54 (d, J C-P = 6.8Hz), 128.26, 128.07 (d, J C-P = 3.5 Hz), 127.77, 127.58, 127.25, 126.08 (d, J C-P = 11.7 Hz).

[0108] Example 20:

[0109]

[0110] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1t (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3t (462 mg), a white solid with a yield of 91%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.45 – 7.39 (m, 1H), 7.38 – 7.20 (m, 17H), 7.12 – 7.07 (m, 1H). 31 P NMR (162 MHz, CDCl3) δ -13.55. 13 C NMR (100 MHz, CDCl3) δ 148.39 (d, J C-P =28.6 Hz), 141.81 (d, J C-P = 6.2 Hz), 137.74 (d, J C-P = 11.6 Hz), 135.94 (d, J C-P = 13.9 Hz), 134.24, 134.03 (d, J C-P = 19.9 Hz), 130.23 (d, J C-P = 4.8 Hz), 129.83 (d, J C-P = 3.8 Hz), 128.83, 128.59, 128.53, 128.46, 127.69, 127.40 (d,J C-P = 18.1 Hz).

[0111] Example 21:

[0112]

[0113] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1u (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3u (517 mg), a white solid with a yield of 94%. The target product was readily oxidized during this process. The product was dissolved in CDCl3, and its structure was characterized by NMR. 1 H NMR (400MHz, CDCl3) δ 7.28 – 7.14 (m, 13H), 7.02 – 6.97 (m, 1H), 6.84 (s, 1H), 6.64(s, 2H), 2.12 (s, 6H). 31 P NMR (162 MHz, CDCl3) δ -13.64. 13 C NMR (100 MHz, CDCl3) δ 148.67 (d, J C-P = 29.4 Hz), 141.68 (d, J C-P = 6.6 Hz), 138.13 (d, J C-P = 11.3 Hz), 137.04, 136.00 (d, J C-P = 13.6 Hz), 134.26, 134.21, 134.01, 130.03(d, J C-P = 5.0 Hz), 128.98, 128.71, 128.52, 128.45, 127.77 (d, J C-P= 3.4 Hz), 127.23.

[0114] Example 22:

[0115]

[0116] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1v (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3v (506 mg), a white solid with a yield of 69%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 8.70 – 8.58 (m, 4H), 8.32 (t, J = 1.9 Hz, 1H), 7.70 – 7.63 (m,4H), 7.62 – 7.54 (m, 2H), 7.51 (td, J = 7.4, 1.3 Hz, 1H), 7.42 – 7.28 (m,12H), 7.22 – 7.17 (m, 1H). 31 P NMR (162 MHz, CDCl3) δ -13.49. 13 C NMR (100 MHz, CDCl3) δ 148.54, 148.25, 140.44 (d, J C-P = 6.6 Hz), 138.12 (d, J C-P = 11.6 Hz), 135.88 (d, J C-P = 14.3 Hz), 134.82, 134.16 (d, JC-P = 19.8 Hz), 130.52 (d, J C-P = 5.0 Hz), 130.00 (d, J C-P = 3.8 Hz), 129.88 (d, J C-P = 12.9 Hz), 129.03, 128.94 (d, J C-P = 3.9 Hz), 128.76, 128.68 (d, J C-P = 4.4 Hz), 128.46 (d, J C-P =1.9 Hz), 127.72, 127.28 (d, J C-P = 1.8 Hz), 127.13 (d, J C-P = 7.8 Hz), 125.31(d, J C-P = 5.3 Hz), 123.66, 123.45 (d, J C-P = 13.7 Hz), 123.19 (d, J C-P = 6.5 Hz).

[0117] Example 23:

[0118]

[0119] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1w (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2a (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3w (406 mg), a white solid with a yield of 71%. The target product was readily oxidized during this process. The product was dissolved in CDCl3, and its structure was characterized by NMR. 1 H NMR (400MHz, CDCl3) δ 7.36 – 7.32 (m, 2H), 7.30 – 7.25 (m, 6H), 7.25 – 7.18 (m, 5H), 7.07 (d, J = 7.4 Hz, 2H), 7.02 (dd, J = 7.7, 3.8 Hz, 1H), 6.62 (d, J = 8.2Hz, 2H), 2.92 (s, 6H). 31 P NMR (162 MHz, CDCl3) δ -13.84. 13 C NMR (100 MHz, CDCl3) δ 149.71, 148.98, 148.68, 138.47 (d, J C-P = 12.1 Hz), 135.69 (d, J C-P =12.8 Hz), 134.61, 133.97 (d, J C-P = 19.6 Hz), 130.62 (d, J C-P = 4.0 Hz), 130.38(d, J C-P = 5.0 Hz), 128.83, 128.48, 128.41, 126.77, 111.69, 40.66.

[0120] Example 24:

[0121]

[0122] In a glove box, add the following raw materials to a 50 mL sealed tube: JPP-1x (1.5 mmol, 1.0 eq.), ethylene glycol dimethyl ether nickel bromide (0.3 mmol, 93 mg, 0.2 eq.), potassium tert-butoxide (4.5 mmol, 505 mg, 3.0 eq.), and diphenylphosphine oxide JPP-2b (4.5 mmol, 909 mg, 3.0 eq.). Add the solvent DMA (12.0 mL), followed by the slow addition of phenylsilane diluted with a small amount of DMA (6.0 mmol, 649 mg, 4.0 eq.). This process is exothermic. After the addition is complete, seal the tube and heat and stir at 130°C for 24 hours. h; Sampling was performed on a TLC plate (using hexane:ethyl acetate = 20 / 1 and hexane:ethyl acetate = 1 / 2 as the developing solvent) or monitored by GC. After the reaction was complete, water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a brown oily liquid. This liquid was then rapidly separated and purified by column chromatography (automatic column chromatography) to obtain the target product JPP-3x (379 mg), a white solid with a yield of 69%. The target product was readily oxidized during this process. The structure of the product was characterized by NMR analysis using CDCl3 to dissolve it. 1 H NMR (400MHz, CDCl3) δ 7.64 – 7.54 (m, 4H), 7.45 (t, J = 7.6 Hz, 2H), 7.42 – 7.34 (m,3H), 7.29 (t, J = 7.7 Hz, 4H), 7.19 (d, J = 7.7 Hz, 4H), 2.38 (s, 6H). 31 P NMR (162 MHz, CDCl3) δ -7.73. 13 C NMR (100 MHz, CDCl3) δ 141.34, 140.70, 138.92,136.82 (d, J C-P = 10.2 Hz), 134.02 (d, J C-P = 19.2 Hz), 133.93 (d, J C-P = 19.7Hz), 133.77 (d, J C-P = 8.7 Hz), 129.49 (d, J C-P= 7.3 Hz), 128.93, 127.61,127.24, 127.18, 21.46。

Claims

1. A method for synthesizing arylphosphine compounds from aryl trifluoromethoxy ethers using nickel catalysis, characterized in that, The arylphosphine compound JPP-3 was prepared by coupling reaction of aryltrifluoromethoxy ether compound JPP-1 and diphenylphosphine oxide compound JPP-2 in the presence of a nickel catalyst, a reducing coupling agent phenylsilane, and a base. ， Ar is a monosubstituted phenyl group, with the following structural formula: ; L is independently selected from phenyl, substituted phenyl. , diphenylamine or ; When L is a substituted phenyl group, the substituent on the ring of the substituted phenyl group is one or more, and is a C1-C3 alkyl, phenyl, or diphenylamino group. pyridine, hydroxyl or dimethylamino; R1 is hydrogen or a C1-C3 alkyl group; when R1 is a C1-C3 alkyl group, L is a phenyl group. The nickel catalyst is nickel bromide in ethylene glycol dimethyl ether.

2. The preparation method according to claim 1, characterized in that, The group structures defined in compounds JPP-1 and JPP-2 are determined by referring to the specific structure of compound JPP-3 and the above coupling reaction. The arylphosphine compound JPP-3 prepared by the coupling reaction is selected from the following compounds: .

3. The preparation method according to claim 1, characterized in that, The base is NaOH, NaOAc, NaH, KOH, t-BuOK, t-BuOLi, or t-BuONa.

4. The preparation method according to claim 1, characterized in that, The molar equivalent ratio of the aryl trifluoromethoxy ether compound JPP-1, the diphenylphosphine oxide compound JPP-2, the base, and the reducing coupling reagent is 1:3:3:

4.

5. The preparation method according to claim 1, characterized in that, The reaction temperature for the coupling reaction is 80-150℃.

6. The preparation method according to claim 1, characterized in that, The reaction time for the coupling reaction is 16-32 hours.

7. The preparation method according to claim 1, characterized in that, The coupling reaction requires the addition of solvent DMA to the reaction system, followed by the slow addition of a small amount of DMA-diluted reducing coupling agent PhSiH3 to the system.

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