Method for constructing aryl C-P bond through reaction of Ar-F compound of electron donating group catalyzed by nickel

Abstract

The invention provides a method for constructing an aryl C-P bond through a reaction of an Ar-F compound of a nickel catalysis electron donating group, which comprises the following steps: in the presence of a nickel catalyst, an additive and alkali, carrying out a coupling reaction on a substituted aryl compound in a formula B and a compound in a formula C diphenylphosphine oxide in an organic solvent to generate an aryl phosphine oxide compound in a formula A, the reaction formula is shown in the specification, Ar is or, and R is an electron-donating group. The method disclosed by the invention has the effects that the substrate has universality, the operation is simple, the condition is mild, a noble metal catalyst and a phosphine ligand are not needed, the cost is low, and the yield is high.

Description

Technical Field

[0001] This invention relates to the field of organophosphine synthesis technology, and more particularly to a method for constructing aryl CP bonds through a nickel-catalyzed reaction of an electron-donating Ar-F compound. Background Technology

[0002] Organophosphorus compounds have attracted considerable attention from researchers due to their wide applications in organic synthesis, medicinal chemistry, and materials science. Over the past few decades, researchers have vigorously developed and refined various synthetic methods for organophosphorus compounds. Currently, arylphosphine ligands are an extremely important class of ligands in metal-catalyzed reactions, thus drawing particular attention to this class of ligands. The Arbuzov or Hirao cross-coupling reaction of aryl halides with phosphorus nucleophiles catalyzed by transition metals provides an efficient synthetic route for the synthesis of arylphosphine ligands and their derivatives. In 1981, Professor Toshikazu Hirao of Osaka University, Japan, developed the Hirao cross-coupling reaction. Aryl halides, sulfonates, diazonium salts, boric acids, silanes, organobismuth reagents, neopentyl esters, thioethers, and other compounds can undergo CX, CO, CN, CB, C-Bi, C-Si, and CS bond cleavage under the action of Pd, Ni, or Cu catalysts to form CP bonds, becoming an important method for the preparation of organophosphine compounds. Among these, CX bonds, in particular, have gained favor among researchers due to their widespread applicability. XI, X-Br, and X-Cl have been extensively reported, while CF bonds have been rarely reported, mainly because typical CF bonds are difficult to activate via transition metal oxidative addition. For example, in 2012, Herzon's group (10.1021 / ol301831k) reported a Pd-catalyzed method for constructing arylphosphine ligands from Ph-I. They used a catalyst formed from 1 mol% Pd2dba3 and Xantphos, effectively coupling common aryl iodides with secondary phosphine oxides, demonstrating the application of this method in the synthesis of novel P-chiral phosphine compounds and phosphine ligands.

[0003] Transition metal-catalyzed coupling reactions, as the most powerful and reliable tools for the formation of carbon-carbon and carbon-heteroatom bonds, have occupied an important position in research. Since their discovery, they have played a significant role in academia and the development of sustainable processes. Richard Heck, Eiichi Negishi, and Akira Suzuki, as outstanding representatives in this field, were awarded the 2010 Nobel Prize in Chemistry for their pioneering contributions to Pd-catalyzed cross-coupling reactions in organic synthesis. On the other hand, the pursuit of versatility and low cost has spurred interest in relatively inexpensive transition metal-rich aryl halide cross-coupling reactions. Nickel-catalyzed systems have been considered suitable alternatives to Cu and Pd in ​​transition metal-catalyzed cross-coupling reactions because they are cost-effective and perform comparable to or better in activating less reactive aryl halides. Furthermore, the multivalent states of Ni allow the reaction to proceed along multiple pathways. However, reductive elimination in nickel-catalyzed systems is often challenging, and the stability of zero-valent nickel has limited the development and application of this field to some extent.

[0004] In summary, we aim to construct a method for synthesizing a class of organophosphine reagents based on Hirao cross-coupling, with the CF bond as the core, and inexpensive Ni compounds as catalysts. In 2020, Angewandte Chemie reported a method from Masaya Sawamura's group to construct CP bonds between inactive Ar-F substrates and phosphine oxyphosphates via KHMDS (Angew. Chem. Int. Ed. 10.1002 / anie.202013544). However, electron-rich Ar-F and Ph-F substrates did not react. Furthermore, using weak bases such as potassium tert-butoxide, potassium methoxide, and potassium carbonate instead of KHMDS yielded poor results.

[0005] In 2022, Professor Zhou Yongbo's research group at Hunan University (Org. Biomol. Chem., 2023, 21, 494–498) proposed a method to obtain CP bonds by reacting electron-withdrawing molecules such as diphenylphosphine oxide and 1-fluoronaphthalene with potassium tert-butoxide and Ni(COD) in toluene. This method is only applicable to Ar-F compounds containing electron-withdrawing groups, but it is largely ineffective for Ar-F compounds with electron-donating groups. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a method for constructing aryl CP bonds through the reaction of nickel-catalyzed electron-donating Ar-F compounds, which solves the problem in existing technologies where electron-donating groups do not react or have low yields in this type of reaction.

[0007] This invention provides a method for constructing aryl CP bonds through a nickel-catalyzed reaction of an electron-donating Ar-F compound, comprising the following steps: in the presence of a nickel catalyst, an additive, and a base, a substituted aromatic compound of formula B and a compound of formula C, diphenylphosphine oxide, are coupled in an organic solvent to generate an aromatic phosphine oxide compound of formula A, as shown in the following reaction formula:

[0008] ,

[0009] Wherein, Ar is or R is an electron-donating group.

[0010] More preferably, the aromatic ring of the compound of formula B includes one or more substituents in addition to F substitution, wherein the substituents are alkyl, alkoxy, pyrrole, amide or amino.

[0011] Most preferably, the compound of formula A is selected from the following compounds:

[0012] , , , , , , , , , .

[0013] It is understood that when the aromatic ring of the compound of formula B has one or more substituents, the substituents are para, ortho, or meta relative to R.

[0014] It is understood that when the aromatic ring of the compound of formula B has multiple substituents, the multiple substituents may be the same or different.

[0015] As used herein, alkyl groups are preferably alkyl groups having 1 to 10 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, etc.; more preferably, alkyl groups having 1 to 4 carbon atoms.

[0016] As used herein, alkoxy groups are preferably alkoxy groups having 1 to 10 carbon atoms, including but not limited to methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, sec-butoxy, etc.; more preferably, alkoxy groups having 1 to 4 carbon atoms.

[0017] Furthermore, the nickel catalyst is nickel bromide in ethylene glycol dimethyl ether.

[0018] Furthermore, the base is potassium tert-butoxide.

[0019] Furthermore, the additive is zinc.

[0020] Furthermore, the organic solvent is dimethylacetamide.

[0021] Furthermore, the molar equivalent ratio of the substituted aromatic compound to diphenylphosphine oxide is 1:3; the molar equivalent ratio of the base to the substituted aromatic compound is 3:1; and the volume of the organic solvent is 8V based on the molar equivalent of the substituted aromatic compound.

[0022] Furthermore, in molar equivalent percentage, the amount of the nickel catalyst is 20% of the substituted aromatic compound; and the amount of the zinc is 100% of the substituted aromatic compound.

[0023] Furthermore, the reaction temperature is 130℃ and the reaction time is 16-24h.

[0024] In this article, the term "equiv." refers to molar equivalent, and "V" refers to solvent volume. For example, 10V means that the solvent volume is 10 times the molar equivalent of the solute, with each mole corresponding to one liter. Specifically, the molar equivalent of the solute is 1 equiv., the solvent volume is 10V, and the concentration is 0.1 mol / L.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The substrates of this invention have good universality, which expands the range of substrates for the formation of CP bonds in the Hirao reaction. In particular, the focus on Ar-F compounds based on electron-donating groups is a breakthrough in participating in the reaction to build CP bonds.

[0027] (2) The method of the present invention does not require the addition of ligands and precious metal palladium, but only uses a low-cost and stable nickel catalyst, which is low in cost;

[0028] (3) The reaction involved in the method of the present invention does not require a superbase reagent, the reaction conditions are relatively mild, it does not require ultraviolet light irradiation, it has a wider range of applications, and it is simple to operate. Detailed Implementation

[0029] To further understand the present invention, the following detailed description, in conjunction with embodiments, illustrates a method for constructing aryl CP bonds via a nickel-catalyzed reaction of an electron-donating Ar-F compound. It should be understood that these embodiments are merely for further detailing the features of the invention and are not intended to limit the scope of the invention or the scope of the claims.

[0030] Example 1 Synthesis

[0031]

[0032] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (catalyst) and dimethyl ethylene glycol bromide (catalyst), 1 eq. of zinc powder, 1.0 eq. of 2,3-dimethylfluorobenzene (reactant formula B1), and 3.0 eq. of diphenylphosphine oxide (reactant formula C1) were added to a 50 mL sealed tube with a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A1, in 38% yield. 1 H NMR (400 MHz, Chloroform-d) δ 7.62-7.54 (m, 4H), 7.50-7.43 (m,2H), 7.42-7.35 (m, 4H), 7.26-7.22 (m, 1H), 6.99-6.92 (m, 1H), 6.78 (dd, J1 =14.1 Hz, J2= 7.7 Hz, 1H), 2.31 (s, 3H), 2.21 (s, 3H). 31 P NMR (162 MHz, Chloroform-d) δ 32.88. LCMS (ESI) m / z calcd for C 20 H 19 OP [M+H] + 307.1, found:307.2.

[0033] Example 2 Synthesis

[0034]

[0035] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of zinc powder (additive), 1.0 eq. of compound B2 (p-1-ethyl-4-fluorobenzene), and 3.0 eq. of compound C2 (diphenylphosphine oxide) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A2, in 74% yield. 1H NMR (400 MHz, Chloroform-d) δ 7.60-7.50 (m, 4H), 7.48-7.41 (m,2H), 7.38-7.32 (m, 2H), 7.30-7.21 (m, 4H), 7.18-7.05 (m, 2H), 2.51 (s, 2H),1.07 (s, 3H). 31 P NMR (162 MHz, Chloroform-d) δ 29.16. LCMS (ESI) m / z calcdfor C 20 H 19 OP [M+H] + 307.1, found: 307.2.

[0036] Example 3 Synthesis

[0037]

[0038] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of Zn powder (additive), 1.0 eq. of p-4-fluoro-1,2-dimethylbenzene (reactant formula B3), and 3.0 eq. of diphenylphosphine oxide (reactant formula C3) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A3, in 62% yield. 1 H NMR (400 MHz, Chloroform-d) δ 7.59-7.50 (m, 5H), 7.44-7.37(m, 1H), 7.37-7.31 (m, 2H), 7.31-7.26 (m, 3H), 7.22-7.16 (m, 1H), 7.05 (dd,J1 = 7.7 Hz, J2= 3.3 Hz, 1H), 2.13 (s, 1H), 2.10 (s, 1H). 31 P NMR (162 MHz, Chloroform-d) δ 29.07. LCMS (ESI) m / z calcd for C 20 H 19 OP [M+H] +307.1, found:307.2.

[0039] Example 4 Synthesis

[0040]

[0041] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of Zn powder (additive), 1.0 eq. of compound B4 (p-5-fluoro-1-methyl-1H-indole), and 3.0 eq. of compound C4 (diphenylphosphine oxide) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A4, in 76% yield. 1 H NMR (400 MHz, Chloroform-d) δ 7.91 (d, J = 12.8 Hz, 1H), 7.73-7.66 (m, 4H), 7.56-7.47 (m, 3H), 7.47-7.38 (m, 5H), 7.12 (d, J = 3.1 Hz, 1H), 6.54-6.48 (m, 1H), 3.82 (s, 3H). 31 P NMR (162 MHz, Chloroform-d) δ 31.09.LCMS (ESI) m / z calcd for C 21 H 18 NOP [M+H] + 332.1, found: 332.2.

[0042] Example 5 Synthesis

[0043]

[0044] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of Zn powder (additive), 1.0 eq. of p-4-fluoro-N,N-dimethylaniline (reactant formula B5), and 3.0 eq. of diphenylphosphine oxide (reactant formula C5) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A5, in 44% yield. 1 H NMR (400 MHz, Chloroform-d) δ 7.71-7.64 (m, 4H), 7.52-7.40 (m, 8H), 6.74-6.67 (m, 2H), 3.01 (s, 6H). 31 P NMR (162 MHz, Chloroform-d) δ 29.51. LCMS (ESI) m / z calcd for C 20 H 20 NOP [M+H] + 322.1, found: 332.2.

[0045] Example 6 Synthesis

[0046]

[0047] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of Zn powder (additive), 1.0 eq. of p-2-fluoro-5-methylpyridine (reactant formula B6), and 3.0 eq. of diphenylphosphine oxide (reactant formula C6) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A6, in 55% yield. 1H NMR (400 MHz, Chloroform-d) δ 8.60 (s, 1H), 8.21-8.15 (m, 1H), 7.91-7.81 (m, 4H), 7.67-7.59 (m, 1H), 7.54-7.36 (m, 6H), 2.37 (s, 3H). 31 P NMR (162 MHz, Chloroform-d) δ 21.22. LCMS (ESI) m / z calcd for C 18 H 16 NOP [M+H] + 294.1, found: 294.2.

[0048] Example 7 Synthesis

[0049]

[0050] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of zinc powder (additive), 1.0 eq. of p-N-ethyl-4-fluoro-N-methylphenethylamine (reactant formula B7), and 3.0 eq. of diphenylphosphine oxide (reactant formula C7) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A7, in 45% yield. 1 H NMR (400 MHz, Chloroform-d) δ 7.72-7.57 (m, 6H),7.57-7.50 (m, 2H), 7.49-7.40 (m, 6H), 3.53 (s, 2H), 2.50-2.41 (m, 2H), 2.19(s, 3H), 1.13-1.06 (m,3H). 31 P NMR (162 MHz, Chloroform-d) δ 29.22. LCMS (ESI)m / z calcd for C 22 H 24 NOP [M+H] + 350.2, found: 350.3.

[0051] Example 8 Synthesis

[0052]

[0053] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of zinc powder (additive), 1.0 eq. of N,N-diethyl-6-fluoropyridine-3-amine (reactant formula B8), and 3.0 eq. of diphenylphosphine oxide (reactant formula C8) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A8, in 56% yield. 1 H NMR (400 MHz, Chloroform-d) δ 8.22 (d, J = 3.0 Hz,1H), 7.97 (dd, J1 = 8.8 Hz, J2= 5.1 Hz, 1H), 7.87-7.78 (m, 3H), 7.48-7.35 (m,6H), 6.91 (dt, J1 = 8.8 Hz, J2= 3.0 Hz, 1H), 3.36 (q, J = 7.1 Hz, 4H), 1.15(t, J = 7.1 Hz, 6H). 31 P NMR (162 MHz, Chloroform-d) δ 22.38. LCMS (ESI) m / zcalcd for C 21 H 23 N2OP [M+H] + 351.2, found: 351.2.

[0054] Example 9 Synthesis

[0055]

[0056] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of Zn powder (additive), 1.0 eq. of p-2-fluoro-5-methoxypyridine (reactant formula B9), and 3.0 eq. of diphenylphosphine oxide (reactant formula C9) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A9, in 52% yield. 1 H NMR (400 MHz, Chloroform-d) δ 8.39 (s, 1H), 8.18-8.12 (m,1H), 7.77 (dd, J1 = 12.0 Hz, J2= 7.6 Hz, 4H), 7.45-7.31 (m, 6H), 7.24-7.17(m, 1H), 3.79 (s, 1H). 31 P NMR (162 MHz, Chloroform-d) δ 21.44. LCMS (ESI) m / zcalcd for C 18 H 16 NO2P [M+H] + 310.1, found: 310.2.

[0057] Example 10 Synthesis

[0058]

[0059] Under N2 protection, 3.0 eq. of potassium tert-butoxide (organic base), 0.2 eq. of nickel bromide (ethylene glycol dimethyl ether) (catalyst), 1 eq. of Zn powder (additive), 1.0 eq. of p-N-(4-fluorophenyl)-N-methylacetamide (reactant formula B10), and 3.0 eq. of diphenylphosphine oxide (reactant formula C10) were added to a 50 mL sealed tube containing a stir bar. Then, DMA (8V) solvent was added, and the reaction was carried out at 130 °C for 16 h. The mixture was then cooled to room temperature, the reaction was quenched with water, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried over anhydrous sodium sulfate, and evaporated to dryness before being passed through a silica gel column (eluent: MeOH:DCM = 1 / 50-1 / 20) to obtain the pure product, compound A10, in 75% yield. 1H NMR (400 MHz, Chloroform-d) δ 7.71-7.59 (m,6H), 7.58-7.52 (m, 2H), 7.51-7.43 (m, 4H), 7.35-7.27 (m, 2H), 4.64 (s, 2H),2.95 (s, 3H), 2.17 (s, 3H). 31 P NMR (162 MHz, Chloroform-d) δ 29.11. LCMS(ESI) m / z calcd for C 22 H 22 NO2P [M+H] + 364.1, found:364.2。

Claims

1. A method for constructing an aryl CP bond by a nickel-catalyzed reaction of an electron-donating Ar-F compound, comprising the following steps: In the presence of a nickel catalyst, additives, and a base, a substituted aromatic compound of formula B and a compound of formula C, diphenylphosphine oxide, undergo a coupling reaction in an organic solvent to generate an aromatic phosphine oxide compound of formula A. The reaction equation is as follows: ， Wherein, Ar is or R is an electron-donating group.

2. The method for constructing aryl CP bonds by a nickel-catalyzed electron-donating Ar-F compound reaction as described in claim 1, characterized in that: In addition to F substitution, the aromatic ring of compound B also includes one or more substituents, which are alkyl, alkoxy, pyrrole, amide, or amino groups.

3. The method for constructing aryl CP bonds by a nickel-catalyzed reaction of an electron-donating Ar-F compound as described in claim 1, characterized in that: The aromatic phosphine oxygen type A compound is selected from the following compounds: 、 、 、 、 、 、 、 、 、 。 4. The method for constructing aryl CP bonds by a nickel-catalyzed reaction of an electron-donating Ar-F compound as described in claim 1, characterized in that: The nickel catalyst is nickel bromide in ethylene glycol dimethyl ether.

5. The method for constructing aryl CP bonds by a nickel-catalyzed reaction of an electron-donating Ar-F compound as described in claim 1, characterized in that: The additive is zinc.

6. The method for constructing aryl CP bonds by a nickel-catalyzed electron-donating Ar-F compound reaction as described in claim 1, characterized in that: The alkali is potassium tert-butoxide.

7. The method for constructing aryl CP bonds by a nickel-catalyzed reaction of an electron-donating Ar-F compound as described in claim 1, characterized in that: The organic solvent is dimethylacetamide.

8. The method for constructing aryl CP bonds by a nickel-catalyzed reaction of an electron-donating Ar-F compound as described in claim 1, characterized in that: The molar equivalent ratio of the substituted aromatic compound to diphenylphosphine oxide is 1:3; the molar equivalent ratio of the base to the substituted aromatic compound is 3:1; and the volume of the organic solvent is 8V based on the molar equivalent of the substituted aromatic compound.

9. A method for constructing aryl CP bonds by a nickel-catalyzed, electron-donating Ar-F compound reaction as described in claim 1 or 5, characterized in that: The amount of nickel catalyst used is 20% of the substituted aromatic compound, and the amount of zinc used is 100% of the substituted aromatic compound, based on molar equivalent percentage.

10. The method for constructing aryl CP bonds by a nickel-catalyzed electron-donating Ar-F compound reaction as described in claim 1, characterized in that: The reaction temperature is 130℃ and the reaction time is 16-24h.

Images