A method for photocatalytic synthesis of phosphorylated heteroaromatic hydrocarbons

Abstract

The application discloses a method for photocatalytic synthesis of phosphoracylated heterocyclic aromatic hydrocarbons. In the application, a transition metal cobalt catalyst is used as a photocatalyst, and phosphoracylated heterocyclic aromatic hydrocarbons are successfully synthesized without the assistance of an additional oxidant. The cobalt catalyst exhibits excellent catalytic performance in the photocatalytic synthesis. The synthesis strategy uses a cobalt catalyst, and has the advantages of mild reaction conditions, no need of an additional oxidant, wide substrate applicability, high reaction efficiency and only hydrogen or methane as a byproduct.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis. More specifically, it relates to a method for the photocatalytic synthesis of phosphorylated heterocyclic aromatic hydrocarbons. Background Technology

[0002] Phosphorylated heterocyclic aromatic hydrocarbons are an important class of compounds widely found in nature, with broad applications in organic synthesis, materials science, medicinal chemistry, and bioscience. The construction of phosphorylated heterocyclic aromatic hydrocarbons via the addition of phosphorus (P) radicals to radical acceptors has attracted widespread attention from chemists. In 2014, Studer et al. used isocyanate compounds as P radical acceptors to construct phosphorylated phenanthridine structures (Org. Lett. 2014, 16, 250–253). In 2016, Lu et al. used isocyanate compounds as P radical acceptors to construct phosphorylated phenanthridine and isoquinoline structures via photocatalysis. Isocyanate compounds, as excellent radical acceptors, are widely used to construct high-value heterocyclic aromatic hydrocarbons such as phenanthridine, benzothiazole, and isoquinoline. On the other hand, the use of heterocyclic aromatic hydrocarbons as P radical acceptors has also been extensively studied. In 2006, Zhang et al. used Mn(III) salts as oxidants to oxidize phosphorus oxides to generate P radicals, which then added to heterocyclic aromatics to yield phosphorylated heterocyclic aromatics (Org. Lett. 2006, 8, 23, 5291–5293). In 2021, Lei et al. used an electrochemical method to oxidize phosphorus oxides to generate P radicals, which then added to heterocyclic aromatics to yield phosphorylated heterocyclic aromatics (ACS Catal. 2021, 4295–4300). Nevertheless, the use of precious metal catalysts and harsh reaction conditions significantly limit the application of these methods. Exploring mild, green, inexpensive, and atom-economical synthetic methods for phosphorylated heterocyclic aromatics is important and necessary. Although visible light photocatalysis can synthesize phosphorylated heterocyclic aromatics under mild reaction conditions, these reactions require the participation of stoichiometric oxidants (J. Am. Chem. Soc. 2021, 143, 964–972) and generate a large number of byproducts. Summary of the Invention

[0003] To address the aforementioned problems, the present invention aims to provide a method for the photocatalytic synthesis of phosphorylated heterocyclic aromatic hydrocarbons. Specifically, this method utilizes a single photocatalyst to catalytically oxidize a phosphorus-oxygen substrate under visible light to generate a P radical, which then undergoes radical addition to a radical acceptor to ultimately yield the phosphorylated heterocyclic aromatic hydrocarbon product.

[0004] To achieve the above objectives, this invention discloses a method for photocatalytic synthesis of phosphorylated heterocyclic aromatic hydrocarbons, comprising the following steps:

[0005] A cobalt catalyst, a phosphorus oxide compound, and a free radical acceptor are added to a solvent to obtain solution A. Solution A is then irradiated with visible light in an inert gas atmosphere to obtain a phosphorylated heterocyclic aromatic compound.

[0006] The phosphorus oxide compound is selected from compounds shown in Formula I below;

[0007]

[0008] The free radical acceptor is an isocyanate compound or a heteroatom aromatic hydrocarbon compound; the isocyanate compound is selected from one of the compounds shown in Formulas II to IV and Compounds 1 to 5 below;

[0009]

[0010] The heteroatomic aromatic hydrocarbon is selected from one of the compounds shown in Formula V and Compounds 6 to 11 below;

[0011]

[0012] In this context, R1 and R2 each independently represent carbon atoms with numbers C1 to C2. 20 The alkyl group has a carbon number of C1 to C2. 20 One of the following: alkoxy group, substituted or unsubstituted thiophene ring, substituted or unsubstituted furan ring, substituted or unsubstituted pyrrole ring, substituted or unsubstituted pyridine ring, substituted or unsubstituted phenyl group, or substituted or unsubstituted naphthyl group; R1 and R2 may be the same or different;

[0013] R3 to R8 each independently represent H, and the number of carbon atoms is C1 to C8. 20 The alkyl group has a carbon number of C1 to C2. 20 The alkoxy group has a carbon number of C1 to C2. 20 One of the following groups: ester group, F, Cl, Br, CN, CH2F, CHF2, CF3, OCF3, OCHF2, or OCH2F; R3 to R8 may be the same or different;

[0014] R9, R 10 Each independently represents H, and the number of carbon atoms is C1 to C2. 20 The alkyl group has a carbon number of C1 to C2. 20 The alkoxy group has a carbon number of C1 to C2. 20 One of the following: ester group, F, Cl, Br, OCF3, OCHF2, OCH2F, CH2F, CHF2, or CF3; R9 and R 10 They can be the same or different;

[0015] R 11 ~R 13 Each independently represents H, and the number of carbon atoms is C1 to C2. 20The alkyl group has a carbon number of C1 to C2. 20 One of the following: alkoxy group, F, Cl, Br; R 11 ~R 13 They can be the same or different;

[0016] R 14 ~R 16 Each independently represents H, and the number of carbon atoms is C1 to C2. 20 The alkyl group has a carbon number of C1 to C2. 20 The alkoxy group has a carbon number of C1 to C2. 20 One of the following: ester group, phenyl group, F, Cl, Br, CHO, TMS; R 14 ~R 16 They can be the same or different; X represents S or O.

[0017] In this invention, a cobalt transition metal catalyst was used as a photocatalyst to successfully synthesize phosphorylated heterocyclic aromatic hydrocarbons without the assistance of an additional oxidant. The cobalt catalyst exhibited excellent catalytic performance in the photocatalytic synthesis. This synthetic strategy, using a cobalt catalyst, has advantages such as mild reaction conditions, no need for an additional oxidant, broad substrate applicability, high reaction efficiency, and the only byproduct being hydrogen or methane.

[0018] In this invention, the synthesis process of phosphorylated heterocyclic aromatic hydrocarbons involves photoexcitation of a cobalt catalyst to an excited state under visible light irradiation. The phosphorus oxide is oxidized by the excited-state cobalt catalyst to generate a phosphorus radical, which in turn produces a reduced-state cobalt catalyst. The phosphorus radical then undergoes radical addition with a radical acceptor (isocyanate or heterocyclic aromatic hydrocarbon) to yield a new radical intermediate. The reduced-state cobalt catalyst combines with the radical intermediate, and through a β-H elimination or hydrogen atom transfer process, the phosphorylated heterocyclic aromatic hydrocarbon product is obtained, releasing hydrogen or methane as the sole byproduct to complete the catalytic cycle.

[0019] Furthermore, the substituents of R1 and R2 are selected from H and have a carbon number of C1 to C2. 20 The alkyl group has a carbon number of C1 to C2. 20 One or more of the following: alkoxy group, F or Cl.

[0020] Furthermore, the phosphorus oxide is selected from one of the following compounds:

[0021]

[0022] Furthermore, formulas II to IV are selected from one of the following compounds:

[0023]

[0024]

[0025] Furthermore, formula V is selected from one of the following compounds:

[0026]

[0027] Furthermore, the cobalt catalyst in this invention is introduced to catalyze the recycling of the reaction process. Those skilled in the art can select other suitable cobalt catalysts according to experimental needs, and this invention does not limit this. In one specific embodiment, the cobalt catalyst includes, but is not limited to, one or more of Co(dmgH)2pyCl, Co(dmgBF2)2(H2O)2, Co(dmgH)2Cl2, Co(dmgBF2)2(CH3CN)2, Co(dmgBF2)2(CH3CN)(CH3OH), Co(dmgBF2)2(CH3CN)(H2O), cobalt powder, cobalt acetate, cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt perchlorate; preferably, the catalytic effect is better when the cobalt catalyst is one or more of Co(dmgH)2pyCl, Co(dmgBF2)2(H2O)2, Co(dmgH)2Cl2, Co(dmgBF2)2(CH3CN)2, Co(dmgBF2)2(CH3CN)(CH3OH), and Co(dmgBF2)2(CH3CN)(H2O).

[0028] Furthermore, the solvent in this invention is only for providing a solution environment for the substrate, and the solvent includes, but is not limited to, one or more of dichloromethane, 1,4-dioxane, acetone, diethyl ether, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, N,N-dimethylformamide, dimethylacetamide, toluene, chloroform, dimethyl ether, dichloroethane, and water.

[0029] Furthermore, the solution A also includes an alkaline compound to provide an alkaline environment. The introduction of the alkaline compound is beneficial to the forward reaction. The alkaline compound includes, but is not limited to, one or more of K2CO3, Na2CO3, Cs2CO3, K3PO4, K2HPO4, NaOH, DCBCO, TEA, pyridine, 2,6-dimethylpyridine, or 2,4,6-trimethylpyridine.

[0030] Furthermore, the molar concentration of the cobalt catalyst in solution A is 10. -5 M-1M; exemplarily, the molar concentration of the cobalt catalyst can also be 10. -5 M-10 -1 M, 10 -5 M-10 -2 M, 10 -5 M-10 -3 M, 10 -5 M-10-4 M, 10 -4 M-1M, 10 -4 M-10 -1 M, 10 -4 M-10 -2 M, 10 -4 M-10 -3 M, 10 -3 M-1M, 10 -3 M-10 -1 M, 10 -3 M-10 -2 M, 10 -2 M-1M, 10 -2 M-10 -1 M, 10 - 1 M-1M, etc.

[0031] Further, the molar concentration of the phosphorus oxide compound is 0.001M-10M; exemplaryly, the molar concentration of the phosphorus oxide compound can also be 0.001M-5M, 0.001M-1M, 0.001M-0.5M, 0.001M-0.1M, 0.001M-0.05M, 0.001M-0.01M, 0.001M-0.005M, 0.005M-0.01M, 0.005M-0.05M, 0.005M-0.1M, 0.005M-0.5M, 0.005M-1M, 0.005M-5M. 0.005M-10M, 0.01M-0.05M, 0.01M-0.1M, 0.01M-0.5M, 0.01M-1M, 0.01M-5M, 0.01M-10M, 0.05M-0.1M, 0.05M-0.5M, 0.05M-1M, 0.05M-5M, 0.05M-10M, 0.1M-0.5M, 0.1M-1M, 0.1M-5M, 0.1M-10M, 0.5M-1M, 0.5M-5M, 0.5M-10M, 1M-5M, 1M-10M or 5M-10M, etc.

[0032] Further, the molar concentration of the free radical acceptor is 0.001M-10M; exemplaryly, the molar concentration of the free radical acceptor can also be 0.001M-5M, 0.001M-1M, 0.001M-0.5M, 0.001M-0.1M, 0.001M-0.05M, 0.001M-0.01M, 0.001M-0.005M, 0.005M-0.01M, 0.005M-0.05M, 0.005M-0.1M, 0.005M-0.5M, 0.005M-1M, 0.005M-5M. 0.005M-10M, 0.01M-0.05M, 0.01M-0.1M, 0.01M-0.5M, 0.01M-1M, 0.01M-5M, 0.01M-10M, 0.05M-0.1M, 0.05M-0.5M, 0.05M-1M, 0.05M-5M, 0.05M-10M, 0.1M-0.5M, 0.1M-1M, 0.1M-5M, 0.1M-10M, 0.5M-1M, 0.5M-5M, 0.5M-10M, 1M-5M, 1M-10M or 5M-10M, etc.

[0033] Furthermore, when the concentration ratio of the phosphorus oxide to the free radical acceptor is 1:0.01-100, it is more conducive to the photocatalytic synthesis of phosphorylated heterocyclic aromatic hydrocarbons.

[0034] Furthermore, the visible light source is selected from sunlight, LED lamps, medium-pressure mercury lamps, high-pressure mercury lamps, or xenon lamps.

[0035] The beneficial effects of this invention are as follows:

[0036] 1. This invention reports for the first time a method for photocatalytic synthesis of phosphorylated heterocyclic aromatic hydrocarbons, demonstrating the potential application of this method in the production of phosphorylated heterocyclic aromatic hydrocarbons.

[0037] 2. This invention proposes a photocatalytic oxidation of phosphorus oxides to generate P radicals, which then undergo addition with radical acceptors (isocyanates or heterocyclic aromatics). The product is generated through a β-H elimination process or a hydrogen atom transfer process, providing a general method for synthesizing phosphorylated heterocyclic aromatics without the need for additional oxidants.

[0038] 3. The method provided by this invention can be achieved at room temperature by irradiation with visible light or sunlight, without requiring harsh reaction conditions such as high temperature, high pressure, or additional oxidants. The entire reaction process is green, efficient, and the reaction conditions are very mild. Attached Figure Description

[0039] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0040] Figure 1 This diagram illustrates the mechanism of photocatalytic reaction of cobalt catalysts with phosphorus oxides and isocyanates to synthesize phosphorylated heterocyclic aromatics. Detailed Implementation

[0041] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0042] Any range described in this invention includes the endpoint, any value between the endpoints, and any subrange consisting of the endpoint or any value between the endpoints.

[0043] Example 1

[0044] (1)

[0045] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain phenanthrene-6-yldiphenylphosphine oxide in a yield of 75%.

[0046] 1 H NMR (400MHz, CDCl3) δ9.52(d,J=8.2Hz,1H),8.67(d,J=8.2Hz,1H),8.61(d,J=7.0Hz,1H),8.06(d,J=6. 8Hz,1H),8.01–7.90(m,4H),7.86(t,J=7.6Hz,1H),7.78–7.64(m,3H),7.58–7.49(m,2H),7.45(m,4H).

[0047] Example 2

[0048] (2)

[0049] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻² were added to 4 mL of DCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain (3-methylphenidin-6-yl)diphenylphosphine oxide in a yield of 76%.

[0050] 1 H NMR (400MHz, CDCl3) δ9.51(d,J=8.2Hz,1H),8.59(d,J=8.0Hz,1H),8.45(d,J=8.1Hz,1H),8.03–7.8 9(m,4H),7.85(s,1H),7.81(t,J=7.6Hz,1H),7.65(t,J=7.4Hz,1H),7.58–7.40(m,7H),2.54(s,3H).

[0051] Example 3

[0052] (3)

[0053] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻³ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain (2-methylphenidin-6-yl)diphenylphosphine oxide in 82% yield.

[0054] 1 H NMR (400MHz, CDCl3) δ9.52(d,J=8.2Hz,1H),8.66(d,J=8.2Hz,1H),8.40(s,1H),8.03–7. 92(m,5H),7.85(t,J=7.5Hz,1H),7.70(t,J=7.6Hz,1H),7.58–7.43(m,7H),2.66(s,3H).

[0055] Example 4

[0056] (4)

[0057] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻⁴ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (1-Methylphenidin-6-yl)diphenylphosphine oxide was obtained in 75% yield.

[0058] 1 H NMR (400MHz, CDCl3) δ9.57(d,J=8.1Hz,1H),8.88(d,J=8.5Hz,1H),8.01–7.88(m,J=8.6Hz,5H),7.81 (t,J=7.6Hz,1H),7.68(t,J=7.5Hz,1H),7.62–7.48(m,4H),7.47–7.39(m,J=7.1Hz,4H),3.09(s,3H).

[0059] Example 5

[0060] (5)

[0061] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻⁵ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (4-Methylphenidin-6-yl)diphenylphosphine oxide was obtained in 82% yield.

[0062] 1 H NMR (400MHz, CDCl3) δ9.41(d,J=8.2Hz,1H),8.62(d,J=8.2Hz,1H),8.41(d,J=7.9Hz,1H),8.05–7.84(m,4H),7.80 (t,J=7.4Hz,1H),7.66(t,J=7.5Hz,1H),7.58(t,J=7.5Hz,1H),7.56–7.47(m,3H),7.47-7.38(m,4H),2.48(s,3H).

[0063] Example 6

[0064] (6)

[0065] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻⁶ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (2-(tert-butyl)phenanthrene-6-yl)diphenylphosphine oxide was obtained in 81% yield.

[0066] 1 H NMR (400MHz, CDCl3) δ9.51(d,J=8.2Hz,1H),8.70(d,J=8.2Hz,1H),8.58(s,1H),8.00(d,J=8.6Hz,1H),7.97 –7.86(m,4H),7.88-7.76(m,2H),7.67(t,J=7.6Hz,1H),7.54–7.47(m,2H),7.47–7.38(m,4H),1.48(s,9H).

[0067] Example 7

[0068] (7)

[0069] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻⁷ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (2-Methoxyphenanthrene-6-yl)diphenylphosphine oxide was obtained in 80% yield.

[0070] 1 H NMR(400MHz, CDCl3)δ9.45(d,J=8.2Hz,1H),8.54(d,J=8.2Hz,1H),8.05–7.88(m,5H),7.86(s,1H), 7.78(t,J=7.5Hz,1H),7.65(t,J=7.5Hz,1H),7.55–7.39(m,6H),7.30(d,J=9.0Hz,1H),3.98(s,3H).

[0071] Example 8

[0072] (8)

[0073] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻⁸ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (2-Fluorophydin-6-yl)diphenylphosphine oxide was obtained in a yield of 62%.

[0074] 1 H NMR (400MHz, CDCl3) δ9.54(d,J=8.0Hz,1H),8.53(d,J=8.0Hz,1H),8.20(d,J=9.9Hz,1H),8.12– 8.03(m,1H),8.02–7.91(m,4H),7.87(t,J=7.2Hz,1H),7.74(t,J=7.2Hz,1H),7.62–7.41(m,7H).

[0075] Example 9

[0076] (9)

[0077] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻⁹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (2-Chlorophenonedi-6-yl)diphenylphosphine oxide was obtained in a yield of 57%.

[0078] 1 H NMR (400MHz, CDCl3) δ9.54(d,J=7.0Hz,1H),8.57(s,2H),8.08–7.84(m,6H),7.80–7.71(m,1H),7.67(d,J=8.2Hz,1H),7.62–7.42(m,6H).

[0079] Example 10

[0080] (10)

[0081] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹⁰ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. 6-(diphenylphosphoyl)phenanthrene-2-carboxynitrile was obtained in a yield of 47%.

[0082] 1 H NMR(400MHz, CDCl3)δ9.61(d,J=7.2Hz,1H),8.97(s,1H),8.66(d,J=7.7Hz,1H), 8.16(d,J=7.7Hz,1H),8.08–7.88(m,6H),7.88–7.75(m,1H),7.65–7.44(m,6H).

[0083] Example 11

[0084] (11)

[0085] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹ were added to 4 mL of DCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Methyl 6-(diphenylphosphoyl)phenanthrene-2-carboxylic acid was obtained in a yield of 40%.

[0086] 1 H NMR (400MHz, CDCl3) δ9.54(d,J=8.2Hz,1H),9.34(s,1H),8.76(d,J=8.1Hz,1H),8.31(d,J=8.4Hz,1H),8.09 (d,J=8.2Hz,1H),8.00–7.86(m,5H),7.74(t,J=7.5Hz,1H),7.58–7.42(m,J=21.3,7.0Hz,6H),4.03(s,3H).

[0087] Example 12

[0088] (12)

[0089] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹² were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (8-Methylphenidin-6-yl)diphenylphosphine oxide was obtained in 74% yield.

[0090] 1 H NMR (400MHz, CDCl3) δ9.35 (s, 1H), 8.60-8.51 (m, 2H), 8.04 (d, J = 6.9Hz, 1H) ,8.01–7.90(m,4H),7.67(d,J=5.8Hz,3H),7.56–7.38(m,6H),2.57(s,3H).

[0091] Example 13

[0092] (13)

[0093] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹³ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain (10-methylphenidin-6-yl)diphenylphosphine oxide in a yield of 77%.

[0094] 1 H NMR(400MHz, CDCl3)δ9.46(d,J=7.9Hz,1H),8.95–8.80(m,1H),8.07(d,J=4.2Hz,1H),7.95 –7.86(m,4H),7.70(d,J=7.0Hz,3H),7.60(t,J=7.6Hz,1H),7.56–7.41(m,6H),3.14(s,3H).

[0095] Example 14

[0096] (14)

[0097] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹⁴ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (8-Methoxyphenanthrene-6-yl)diphenylphosphine oxide was obtained in 73% yield.

[0098] 1 H NMR (400MHz, CDCl3) δ9.03 (s, 1H), 8.50 (dd, J = 17.8, 8.4Hz, 2H), 8.04 (d, J = 7.7 Hz,1H),8.01–7.89(m,4H),7.71–7.60(m,2H),7.54–7.40(m,7H),3.93(s,3H).

[0099] Example 15

[0100] (15)

[0101] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹⁵ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain (8-fluorophenanthridine-6-yl)diphenylphosphine oxide in 70% yield.

[0102] 1 H NMR(400MHz, CDCl3)δ9.33(d,J=10.1Hz,1H),8.68–8.58(m,1H),8.51(d,J=6.8Hz,1 H),8.07(d,J=6.8Hz,1H),8.02–7.88(m,4H),7.77–7.65(m,2H),7.62–7.40(m,7H).

[0103] Example 16

[0104] (16)

[0105] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹⁶ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (8-Chlorophenidine-6-yl)diphenylphosphine oxide was obtained in a yield of 63%.

[0106] 1 H NMR(400MHz, CDCl3)δ9.67(s,1H),8.60–8.44(m,2H),8.09–8.02(m,1H),8.0 1–7.88(m,4H),7.75(d,J=8.8Hz,1H),7.73–7.66(m,2H),7.57–7.39(m,6H).

[0107] Example 17

[0108] (17)

[0109] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹⁷ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. (8-Bromophenidine-6-yl)diphenylphosphine oxide was obtained in 61% yield.

[0110] 1 H NMR(400MHz, CDCl3)δ9.83(s,1H),8.57-8.41(m,2H),8.10-8.03(m,1H),8.0 2–7.92(m,4H),7.90(d,J=8.8Hz,1H),7.77–7.66(m,2H),7.60–7.40(m,6H).

[0111] Example 18

[0112] (18)

[0113] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹⁸ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Diphenyl(8-(trifluoromethyl)phenanthrene-6-yl)phosphine oxide was obtained in a yield of 57%.

[0114] 1 H NMR (400MHz, CDCl3) δ10.04(s,1H),8.75(d,J=8.5Hz,1H),8.60(d,J=5.9Hz,1H) ,8.13(d,J=6.0Hz,1H),8.07–7.93(m,5H),7.85–7.73(m,2H),7.57–7.41(m,6H).

[0115] Example 19

[0116] (19)

[0117] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹⁹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by column chromatography. 6-(diphenylphosphoyl)phenanthrene-8-carboxynitrile was obtained in 48% yield.

[0118] 1 H NMR (400MHz, CDCl3) δ10.09(s,1H),8.71(d,J=8.6Hz,1H),8.58(d,J=7.2Hz,1H) ,8.13(d,J=8.3Hz,1H),8.03–7.90(m,5H),7.88–7.76(m,2H),7.59–7.40(m,6H).

[0119] Example 20

[0120] (20)

[0121] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻²⁰ were added to 4 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. [1,3]dioxonium[4,5-j]phenanthridine-6-diphenylphosphine oxide was obtained in 59% yield.

[0122] 1 H NMR (400MHz, CDCl3) δ9.02 (s, 1H), 8.40–8.31 (m, 1H), 8.01 (d, J = 6.3Hz, 1H) ,7.98–7.87(m,5H),7.64(d,J=4.0Hz,2H),7.56–7.35(m,6H),6.10(s,2H).

[0123] Example 21

[0124] (twenty one)

[0125] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻²¹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by column chromatography. (2-Methyl-8-(trifluoromethyl)phenanthrene-6-yl)diphenylphosphine oxide was obtained in 50% yield.

[0126] 1 H NMR (400MHz, CDCl3) δ10.00(s,1H),8.72(d,J=8.6Hz,1H),8.37(s,1H),8.09–7.90(m,6H),7.61(d,J=8.3Hz,1H),7.56–7.40(m,6H),2.64(s,3H).

[0127] Example 22

[0128] (twenty two)

[0129] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻²⁻ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Dibenzo[i,k]phenanthrene-5-yldiphenylphosphine oxide was obtained in a yield of 57%.

[0130] 1 H NMR (400MHz, CDCl3) δ8.45(d,J=8.1Hz,1H),8.32(t,J=7.8Hz,2H),8.25(d,J=8.0Hz,1H),8.09(d,J=8.0Hz,1H),7.73( d,J=7.9Hz,1H),7.64–7.46(m,4H),7.36(t,J=7.4Hz,1H),7.33–7.22(m,3H),7.18(t,J=7.4Hz,1H),7.13–6.93(m,7H).

[0131] Example 23

[0132] (twenty three)

[0133] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A₂, and 0.1 mmol of B₁ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain phenanthridine-6-yldi-o-tolylphosphine oxide in a yield of 48%. 1 H NMR (400MHz, CDCl3) δ9.22(d,J=8.1Hz,1H),8.69(d,J=8.1Hz,1H),8.62(d,J=7.9Hz,1H),7.93(d,J=7.8Hz,1H),7.8 5(t,J=7.4Hz,1H),7.79–7.61(m,3H),7.48–7.34(m,4H),7.31(d,J=3.3Hz,2H),7.16(t,J=6.9Hz,2H),2.46(s,6H).

[0134] Example 24

[0135] (twenty four)

[0136] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A₃⁻, and 0.1 mmol of B₁⁻ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Phenyrin-6-yldi-m-tolylphosphine oxide was obtained in 71% yield. 1 H NMR (400MHz, CDCl3) δ9.52(d,J=8.3Hz,1H),8.64(d,J=8.2Hz,1H),8.61–8.53(m,1H),8.08(d,J=4.9Hz,1H),7.89–7.78(m,3H),7.76–7.62(m 5H),7.36–7.37(m,4H),2.37(s,6H).

[0137] Example 25

[0138] (25)

[0139] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻⁴, and 0.1 mmol of B⁻¹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain phenanthridine-6-yldi-p-tolylphosphine oxide in a yield of 67%. 1 H NMR (400MHz, CDCl3) δ9.51(d,J=8.2Hz,1H),8.62(d,J=8.1Hz,1H),8.60–8.51(m,1H),8.06(d ,J=4.7Hz,1H),7.81(t,J=8.9Hz,5H),7.74–7.59(m,3H),7.24(d,J=7.1Hz,4H),2.36(s,6H).

[0140] Example 26

[0141] (26)

[0142] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻⁵, and 0.1 mmol of B⁻¹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Bis(4-methoxyphenyl)(phenanthridine-6-yl)phosphine oxide was obtained in 72% yield. 1 H NMR (400MHz, CDCl3) δ9.52(d,J=8.2Hz,1H),8.62(d,J=8.1Hz,1H),8.57(d,J=3.3Hz,1H),8.06(d, J=4.3Hz,1H),7.94–7.76(m,5H),7.76–7.55(d,J=5.5Hz,3H),6.95(d,J=8.0Hz,4H),3.80(s,6H).

[0143] Example 27

[0144] (27)

[0145] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻⁶, and 0.1 mmol of B⁻¹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Bis(3,5-dimethylphenyl)(phenanthridine-6-yl)phosphine oxide was obtained in 85% yield. 1 H NMR (400MHz, CDCl3) δ9.50(d,J=8.2Hz,1H),8.62(d,J=8.1Hz,1H),8.56(d,J=5.0Hz,1H),8.08(d,J=4. 8Hz,1H),7.81(t,J=7.3Hz,1H),7.74–7.62(m,3H),7.54(d,J=12.0Hz,4H),7.12(s,2H),2.30(s,12H).

[0146] Example 28

[0147] (28)

[0148] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A₇₃, and 0.1 mmol of B₁₃ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Bis(4-fluorophenyl)(phenanthridine-6-yl)phosphine oxide was obtained in 71% yield. 1 HNMR(400MHz, CDCl3)δ9.48(d,J=8.2Hz,1H),8.66(d,J=8.2Hz,1H),8.64–8.56(m,1H),8.06(d,J =5.1Hz,1H),8.00–7.90(m,4H),7.86(t,J=7.5Hz,1H),7.79–7.65(m,3H),7.15(t,J=8.3Hz,4H).

[0149] Example 29

[0150] (29)

[0151] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻⁸, and 0.1 mmol of B⁻¹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Bis(4-fluorophenyl)(phenanthridine-6-yl)phosphine oxide was obtained in 65% yield. 1 HNMR (400MHz, CDCl3) δ9.45(d,J=8.2Hz,1H),8.66(d,J=8.1Hz,1H),8.60(d,J=4.7Hz,1H ),8.07(d,J=5.0Hz,1H),7.87(t,J=9.4Hz,5H),7.80–7.66(m,3H),7.44(d,J=8.0Hz,4H).

[0152] Example 30

[0153] (30)

[0154] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.15 mmol of K₃PO₄, 0.3 mmol of A⁻⁹, and 0.1 mmol of B⁻¹ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Di(naphthyl-2-yl)(phenanthridine-6-yl)phosphine oxide was obtained in 70% yield. 1 HNMR (400MHz, CDCl3) δ9.55(d,J=8.3Hz,1H),8.63(d,J=8.2Hz,1H),8.58(d,J=13.4Hz,3H),8.04(d,J= 7.4Hz,1H),7.96(t,J=8.9Hz,2H),7.92–7.76(m,7H),7.74–7.62(m,3H),7.51(dt,J=14.8,7.0Hz,4H).

[0155] Example 31

[0156] (31)

[0157] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.3 mmol of TEA, 0.3 mmol of C⁻¹, and 0.1 mmol of B⁻¹ were added to 4 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Ethylphenanthridine-6-yl(phenyl)phosphite was obtained in a yield of 35%. 1 H NMR (400MHz, CDCl3) δ9.33(d,J=8.2Hz,1H),8.64(d,J=8.1Hz,1H),8.58(d,J=6.8Hz,1H),8.23(d,J=7.0Hz,1H),8.12 –8.00(m,2H),7.85(t,J=7.4Hz,1H),7.80–7.68(m,3H),7.58–7.39(m,3H),4.49–4.29(m,2H),1.48(t,J=6.9Hz,3H).

[0158] Example 32

[0159] (32)

[0160] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.20 mmol of Cs₂CO₃, 0.3 mmol of C₂⁻, and 0.1 mmol of B⁻ were added to 4 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain diethyl phenanthridine-6-ylphosphonate in 50% yield. 1 H NMR (400MHz, CDCl3) δ8.97(d,J=8.2Hz,1H),8.65(d,J=8.0Hz,1H),8.59(d,J=7.2Hz,1H),8.30(d,J =7.2Hz,1H),7.87(t,J=7.6Hz,1H),7.81–7.70(m,3H),4.40(q,J=7.2Hz,4H),1.43(t,J=6.9Hz,6H).

[0161] Example 33

[0162] (33)

[0163] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻¹, and 0.1 mmol of D⁻¹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazo-2-yldiphenylphosphine oxide was obtained in 95% yield. 1 H NMR (400MHz, CDCl3) δ8.20 (d, J = 8.1Hz, 1H), 8.06–7.90 (m, 5H), 7.66–7.54 (m, 3H), 7.54–7.44 (m, 5H).

[0164] Example 34

[0165] (34)

[0166] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻¹, and 0.1 mmol of D⁻² were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. (6-Methylbenzo[d]thiazo-2-yl)diphenylphosphine oxide was obtained in a yield >99%. 1HNMR(400MHz, CDCl3) δ8.06(d,J=8.4Hz,1H),7.96(dd,J=12.3,7.7Hz,4H),7.78( s,1H),7.58–7.52(m,2H),7.52–7.43(m,4H),7.34(d,J=8.4Hz,1H),2.49(s,3H).

[0167] Example 35

[0168] (35)

[0169] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻¹, and 0.1 mmol of D⁻³ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. (6-Methoxybenzo[d]thiazolyl)diphenylphosphine oxide was obtained in >99% yield. 1 HNMR(400MHz, CDCl3)δ8.04(d,J=9.0Hz,1H),7.95(dd,J=12.2,7.7Hz,4H),7.59– 7.52(m,2H),7.52–7.44(m,4H),7.40(s,1H),7.14(d,J=9.0Hz,1H),3.87(s,3H).

[0170] Example 36

[0171] (36)

[0172] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻¹, and 0.1 mmol of D⁻⁴ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. (6-fluorobenzo[d]thiazolyl)diphenylphosphine oxide was obtained in 97% yield. 1 H NMR(400MHz, CDCl3)δ8.17–8.10(m,1H),7.96(dd,J=12.4,7.7Hz,4H),7.67(d, J=7.9Hz,1H),7.58(t,J=7.2Hz,2H),7.54–7.44(m,4H),7.28(t,J=8.8Hz,1H).

[0173] Example 37

[0174] (37)

[0175] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻¹, and 0.1 mmol of D⁻⁵ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. (6-chlorobenzo[d]thiazolyl)diphenylphosphine oxide was obtained in 94% yield. 1 H NMR (400MHz, CDCl3) δ8.08 (d, J = 8.8Hz, 1H), 8.02–7.94 (m, 4H), 7.94 (s, 1H), 7.64–7.54 (m, 2H), 7.54–7.40 (t, J = 7.6Hz, 5H).

[0176] Example 38

[0177] (38)

[0178] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻¹, and 0.1 mmol of D⁻⁶ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. (6-Bromobenzo[d]thiazolyl)diphenylphosphine oxide was obtained in 88% yield. 1 H NMR (400MHz, CDCl3) δ8.14(s,1H),8.02(d,J=8.7Hz,1H),8.00–7.90(m,4H),7.63(d,J=8.8Hz,1H),7.58(t,J=7.0Hz,2H),7.54–7.43(m,4H).

[0179] Example 39

[0180] (39)

[0181] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻¹, and 0.1 mmol of D⁻⁷ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Diphenyl(6-(trifluoromethoxy)benzo[d]thiazo-2-yl)phosphine oxide was obtained in 89% yield. 1 H NMR (400MHz, CDCl3) δ8.18(d,J=9.0Hz,1H),7.96(dd,J=12.5,7.7Hz,4H),7.87(s,1H),7.67–7.55(m,2H),7.54–7.46(m,4H),7.41(d,J=8.9Hz,1H).

[0182] Example 40

[0183] (40)

[0184] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻¹, and 0.1 mmol of D⁻⁸ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Diphenyl(5-(trifluoromethyl)benzo[d]thiazo-2-yl)phosphine oxide was obtained in 83% yield. 1 H NMR (400MHz, CDCl3) δ8.47(s,1H),8.13(d,J=8.5Hz,1H),7.98(dd,J=12.6,7.4Hz,4H),7.71(d,J=8.4Hz,1H),7.63–7.55(m,2H),7.55–7.47(m,4H).

[0185] Example 41

[0186] (41)

[0187] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻², and 0.1 mmol of D⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazo-2-yldi-o-tolylphosphine oxide was obtained in 66% yield.1 H NMR(400MHz, CDCl3)δ8.17(d,J=8.0Hz,1H),8.03(d,J=7.9Hz,1H),7.59–7.49(m, 4H),7.46(t,J=7.8Hz,2H),7.33–7.27(m,2H),7.22(t,J=6.8Hz,2H),2.54(s,6H).

[0188] Example 42

[0189] (42)

[0190] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻³, and 0.1 mmol of D⁻¹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazo-2-yldi-m-tolylphosphine oxide was obtained in 85% yield. 1 H NMR (400MHz, CDCl3) δ8.20(d,J=7.8Hz,1H),8.00(d,J=7.5Hz,1H),7.86–7.67(m,4H),7.57–7.29(m,6H),2.37(s,6H).

[0191] Example 43

[0192] (43)

[0193] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A⁻⁴, and 0.1 mmol of D⁻¹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 24 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazo-2-yldi-p-tolylphosphine oxide was obtained in 95% yield. 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.0Hz,1H),7.99(d,J=7.9Hz,1H),7.88–7.78(m,4H ),7.52(t,J=7.5Hz,1H),7.46(t,J=7.4Hz,1H),7.29(d,J=7.5Hz,4H),2.39(s,6H).

[0194] Example 44

[0195] (44)

[0196] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A-5, and 0.1 mmol of D-1 were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazol-2-ylbis(4-methoxyphenyl)phosphine oxide was obtained in 84% yield. 1 HNMR (400MHz, CDCl3) δ8.17(d,J=8.0Hz,1H),7.99(d,J=8.0Hz,1H),7.86(dd,J=11.9 ,8.7Hz,4H),7.49(dt,J=14.9,7.2Hz,2H),6.99(dd,J=8.5,1.7Hz,4H),3.82(s,6H).

[0197] Example 45

[0198] (45)

[0199] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A-6, and 0.1 mmol of D-1 were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazol-2-ylbis(4-fluorophenyl)phosphine oxide was obtained in 86% yield. 1 HNMR (400MHz, CDCl3) δ8.18(d,J=8.0Hz,1H),8.11–7.88(m,5H),7.53(dt,J=14.8,7.2Hz,2H),7.24–7.06(m,4H).

[0200] Example 46

[0201] (46)

[0202] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A-7, and 0.1 mmol of D-1 were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazol-2-ylbis(4-chlorophenyl)phosphine oxide was obtained in 97% yield. 1 H NMR (400MHz, CDCl3) δ8.19(d,J=8.1Hz,1H),8.02(d,J=8.0Hz,1H),7.90(dd,J=12.0,8.3Hz,4H),7.60–7.44(m,6H).

[0203] Example 47

[0204] (47)

[0205] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A-8, and 0.1 mmol of D-1 were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazol-2-ylbis(3,5-dimethylphenyl)phosphine oxide was obtained in 87% yield. 1 H NMR (400MHz, CDCl3) δ8.21(d,J=8.1Hz,1H),8.00(d,J=7.9Hz,1H),7.62–7.51(m,5H),7.47(t,J=7.4Hz,1H),7.18(s,2H),2.33(s,12H).

[0206] Example 48

[0207] (48)

[0208] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.15 mmol of A-9, and 0.1 mmol of D-1 were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazol-2-yldi(naphthyl-2-yl)phosphine oxide was obtained in 97% yield. 1H NMR (400MHz, CDCl3) δ8.60 (d, J = 14.7Hz, 2H), 8.21 (d, J = 8.0Hz, 1H), 8.07–7.96 (m, 3H), 7.96–7.87 (m, 4H), 7.85 (d, J = 7.9Hz, 2H), 7.68–7.41 (m, 6H).

[0209] Example 49

[0210] (49)

[0211] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.30 mmol of TEA, 0.15 mmol of C⁻¹, and 0.1 mmol of D⁻¹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazo-2-yl(phenyl)phosphonate ethyl ester was obtained in a yield of 63%. 1 HNMR (400MHz, CDCl3) δ8.21(d,J=7.8Hz,1H),8.12–8.11(m,2H),7.99(d,J=7.7Hz,1H),7.67–7.44(m,5H),4.43–4.18(m,2H),1.44(t,J=6.7Hz,3H).

[0212] Example 50

[0213] (50)

[0214] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.30 mmol of TEA, 0.15 mmol of C₂⁻, and 0.1 mmol of D⁻¹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazol-2-ylphosphonate diethyl ester was obtained in a yield of 44%. 1 H NMR (400MHz, CDCl3) δ8.24(d,J=8.0Hz,1H),8.00(d,J=7.8Hz,1H),7.62–7.48(m,2H),4.42–4.21(m,4H),1.39(t,J=7.0Hz,6H).

[0215] Example 51

[0216] (51)

[0217] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻¹, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(diphenylphospho)-4-phenylisoquinoline-3-carboxylate was obtained in 81% yield. 1 HNMR(400MHz, CDCl3)δ9.68(d,J=8.2Hz,1H),8.25–8.02(m,4H),7.77–7.61(m,3H),7.58 –7.41(m,9H),7.38–7.28(d,J=2.9Hz,2H),4.11(q,J=6.8Hz,2H),1.04(t,J=7.0Hz,3H).

[0218] Example 52

[0219] (52)

[0220] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻¹, and 0.2 mmol of E⁻² were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Methyl 1-(diphenylphospho)-4-phenylisoquinoline-3-carboxylic acid was obtained in 78% yield. 1 HNMR(400MHz, CDCl3)δ9.67(d,J=8.2Hz,1H),8.32–7.99(m,4H),7.76–7.68(m, 1H),7.67(s,2H),7.57–7.42(m,8H),7.40–7.28(d,J=2.8Hz,2H),3.64(s,3H).

[0221] Example 53

[0222] (53)

[0223] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻¹, and 0.2 mmol of E⁻³ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(diphenylphospho)-7-methyl-4-(p-tolyl)isoquinoline-3-carboxylate was obtained in 88% yield. 1 HNMR(400MHz, CDCl3)δ9.45(s,1H),8.09(dd,J=10.2,8.7Hz,4H),7.59(d,J=8.6Hz,1H),7.54–7.41(m,7H),7.29 (d,J=6.9Hz,2H),7.20(d,J=6.7Hz,2H),4.13(q,J=6.8Hz,2H),2.56(s,3H),2.45(s,3H),1.09(t,J=6.3Hz,3H).

[0224] Example 54

[0225] (54)

[0226] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻¹, and 0.2 mmol of E⁻⁴ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(diphenylphospho)-7-methoxy-4-(4-methoxyphenyl)isoquinoline-3-carboxylic acid was obtained in 74% yield. 1 H NMR(400MHz, CDCl3)δ9.09(s,1H),8.27–8.05(m,4H),7.60(d,J=9.3Hz,1H),7.56–7.42(m,6H),7.28(d,J=9.6Hz,1H) ,7.23(d,J=7.6Hz,2H),7.02(d,J=8.0Hz,2H),4.15(q,J=6.8Hz,2H),3.98(s,3H),3.88(s,3H),1.12(t,J=7.0Hz,3H).

[0227] Example 55

[0228] (55)

[0229] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻¹, and 0.2 mmol of E⁻⁵ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(diphenylphospho)-7-fluoro-4-(4-fluorophenyl)isoquinoline-3-carboxylic acid was obtained in 81% yield. 1 H NMR(400MHz, CDCl3)δ9.48(d,J=10.1Hz,1H),8.19–8.06(m,4H),7.65(d,J=5.6Hz,1H),7.57–7 .40(m,7H),7.32–7.25(m,2H),7.25–7.16(m,2H),4.16(q,J=6.8Hz,2H),1.12(t,J=7.0Hz,3H).

[0230] Example 56

[0231] (56)

[0232] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻¹, and 0.2 mmol of E⁻⁶ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain ethyl 7-bromo-4-(4-bromophenyl)-1-(diphenylphosphoyl)isoquinoline-3-carboxylate in 54% yield. 1 H NMR (400MHz, CDCl3) δ10.02(s,1H),8.18–8.04(m,4H),7.74(d,J=9.0Hz,1H),7.64(d,J=7.7H z,2H),7.57–7.42(m,7H),7.18(d,J=7.6Hz,2H),4.17(q,J=6.8Hz,2H),1.14(t,J=7.0Hz,3H).

[0233] Example 57

[0234] (57)

[0235] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻¹, and 0.2 mmol of E⁻⁷ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(diphenylphospho)-4-methylisoquinoline-3-carboxylate was obtained in 78% yield. 1 H NMR(400MHz, CDCl3)δ9.60(d,J=8.3Hz,1H),8.18(d,J=8.2Hz,1H),8.08–7.95(m,4H),7.79(t,J=7.5Hz, 1H),7.72(t,J=7.3Hz,1H),7.52–7.36(m,6H),4.40(q,J=6.8Hz,2H),2.91(s,3H),1.39(t,J=6.1Hz,3H).

[0236] Example 58

[0237] (58)

[0238] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻¹, and 0.2 mmol of E⁻⁸ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(diphenylphospho)-5,6-dihydro-4H-benzo[de]isoquinoline-3-carboxylate was obtained in 84% yield. 1 H NMR(400MHz, CDCl3)δ9.41(d,J=8.3Hz,1H),8.33–7.97(m,4H),7.61(t,J=7.1Hz,1H),7.56–7.34(m ,7H),4.39(q,J=6.4Hz,2H),3.45(s,2H),3.08(s,2H),2.04(d,J=5.5Hz,2H),1.40(t,J=6.5Hz,3H).

[0239] Example 59

[0240] (59)

[0241] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻², and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(di-o-tolylphosphoryl)-4-phenylisoquinoline-3-carboxylate was obtained in 55% yield. 1 H NMR(400MHz, CDCl3)δ9.24(d,J=6.3Hz,1H),7.70(s,1H),7.69–7.61(m,2H),7.53–7.46(m,3H),7.46–7.39(m,4H),7.3 7(d,J=4.1Hz,2H),7.32–7.26(m,2H),7.19(t,J=7.0Hz,2H),4.01(q,J=6.8Hz,2H),2.46(s,6H),0.95(t,J=6.3Hz,3H).

[0242] Example 60

[0243] (60)

[0244] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻³, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(di-m-tolylphosphoryl)-4-phenylisoquinoline-3-carboxylate was obtained in 79% yield. 1 H NMR(400MHz, CDCl3)δ9.69(d,J=8.3Hz,1H),7.96(d,J=12.1Hz,2H),7.90–7.81(m,2H),7.75–7.60(m, 3H),7.55–7.44(m,3H),7.41–7.28(s,6H),4.13(q,J=6.9Hz,2H),2.39(s,6H),1.06(t,J=6.2Hz,3H).

[0245] Example 61

[0246] (61)

[0247] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻⁴, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(di-p-tolylphosphoryl)-4-phenylisoquinoline-3-carboxylate was obtained in 71% yield. 1 H NMR (400MHz, CDCl3) δ9.69 (d, J = 8.3Hz, 1H), 8.06–7.87 (m, 4H), 7.75–7.67 (m, 1H), 7.64 (s, 2H), 7.53–7.42 ( m,3H),7.36–7.30(m,2H),7.27(d,J=7.4Hz,4H),4.11(q,J=6.8Hz,2H),2.37(s,6H),1.05(t,J=6.1Hz,3H).

[0248] Example 62

[0249] (62)

[0250] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻⁵, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain ethyl 1-(bis(4-methoxyphenyl)phosphoryl)-4-phenylisoquinoline-3-carboxylate in 58% yield. 1 H NMR(400MHz, CDCl3)δ9.69(d,J=8.2Hz,1H),7.99(t,J=9.1Hz,4H),7.75–7.62(m,3H),7.52–7.42(m,3H) ,7.33(d,J=2.8Hz,2H),6.97(d,J=8.7Hz,4H),4.11(q,J=6.9Hz,2H),3.82(s,6H),1.04(t,J=6.1Hz,3H).

[0251] Example 63

[0252] (63)

[0253] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻⁶, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(bis(4-fluorophenyl)phosphoryl)-4-phenylisoquinoline-3-carboxylate was obtained in 90% yield. 1 H NMR (400MHz, CDCl3) δ9.66 (d, J = 8.2Hz, 1H), 8.23–8.02 (m, 4H), 7.78–7.63 (m, 3H), 7.50 (s, 3H) ),7.33(d,J=2.2Hz,2H),7.17(t,J=8.1Hz,4H),4.12(q,J=6.5Hz,2H),1.04(t,J=6.8Hz,3H).

[0254] Example 64

[0255] (64)

[0256] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻⁷, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(bis(4-chlorophenyl)phosphoryl)-4-phenylisoquinoline-3-carboxylate was obtained in 83% yield. 1 H NMR(400MHz, CDCl3)δ9.63(d,J=8.3Hz,1H),8.03(t,J=9.6Hz,4H),7.81–7.64(m,3H), 7.62–7.40(m,7H),7.33(d,J=2.4Hz,2H),4.13(q,J=6.7Hz,2H),1.05(t,J=6.9Hz,3H).

[0257] Example 65

[0258] (65)

[0259] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻⁸, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain ethyl 1-(bis(3,5-dimethylphenyl)phosphoryl)-4-phenylisoquinoline-3-carboxylate in 77% yield. 1 H NMR (400MHz, CDCl3) δ9.70 (d, J = 8.2Hz, 1H), 7.79–7.68 (m, 5H), 7.65 (s, 2H), 7.53–7.44 (m, 3H) ),7.38–7.29(m,2H),7.14(s,2H),4.15(q,J=7.0Hz,2H),2.34(s,12H),1.08(t,J=7.0Hz,3H).

[0260] Example 66

[0261] (66)

[0262] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of K₂CO₃, 0.1 mmol of A⁻⁹, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(bis(naphthyl-2-yl)phosphoryl)-4-phenylisoquinoline-3-carboxylate was obtained in 85% yield. 1 H NMR (400MHz, CDCl3) δ9.74(d,J=8.3Hz,1H),8.72(d,J=13.9Hz,2H),8.16(t,J=8.8Hz,2H),7.92(t,J=7.9Hz,4H),7.85( d,J=7.8Hz,2H),7.77–7.62(m,3H),7.62–7.39(m,7H),7.40–7.29(m,2H),4.09(q,J=6.6Hz,2H),0.98(t,J=7.0Hz,3H).

[0263] Example 67

[0264] (67)

[0265] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of Cs₂CO₃, 0.1 mmol of C⁻¹, and 0.2 mmol of E⁻¹ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(ethoxyphenyl)phosphonyl)-4-phenylisoquinoline-3-carboxylate was obtained in 50% yield. 1 H NMR(400MHz, CDCl3)δ9.37(d,J=8.2Hz,1H),8.19–8.05(m,2H),7.81–7.70(m,1H),7.66(s,2H),7.57–7.4 4(m,6H),7.33(s,2H),4.49–4.28(m,2H),4.19–4.07(m,2H),1.47(t,J=6.5Hz,3H),1.03(t,J=6.6Hz,3H).

[0266] Example 68

[0267] (68)

[0268] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of Cs₂CO₃, 0.1 mmol of C₂⁻, and 0.2 mmol of E⁻ were added to 2 mL of LDCM, and the air atmosphere was replaced with Ar. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Ethyl 1-(dioxophosphoryl)-4-phenylisoquinoline-3-carboxylate was obtained in 44% yield. 1 HNMR(400MHz, CDCl3)δ8.99(d,J=8.3Hz,1H),7.81–7.73(m,1H),7.70(s,2H),7.50(s,3H),7.35 (s,2H),4.54–4.34(m,4H),4.13(q,J=6.8Hz,2H),1.45(t,J=6.9Hz,6H),1.03(t,J=7.0Hz,3H).

[0269] Example 69

[0270] (69)

[0271] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻¹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Diphenyl(thiophene-2-yl)phosphine oxide was obtained in a yield of 56%. 1 HNMR (400MHz, CDCl3) δ7.78–7.67(m,5H),7.56(t,J=7.0Hz,2H),7.52–7.41(m,5H),7.24–7.15(m,1H).

[0272] Example 70

[0273] (70)

[0274] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻² were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. (5-methylthiophene-2-yl)diphenylphosphine oxide was obtained in a yield of 64%. 1 H NMR (400MHz, CDCl3) δ7.92–7.77(m,4H),7.68–7.53(m,6H),7.42–7.31(m,1H),6.95(s,1H),2.63(s,3H).

[0275] Example 71

[0276] (71)

[0277] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻³ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. (5-Methoxythiophene-2-yl)diphenylphosphine oxide was obtained in 53% yield. 1H NMR (400MHz, CDCl3) δ7.84–7.65(m,4H),7.63–7.41(m,6H),7.17–7.00(m,1H),6.29(s,1H),3.91(s,3H).

[0278] Example 72

[0279] (72)

[0280] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻⁴ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Diphenyl(5-phenylthiophene-2-yl)phosphine oxide was obtained in a yield of 72%. 1 H NMR (400MHz, CDCl3) δ7.85–7.72(m,4H),7.63–7.53(m,4H),7.52–7.44(m,4H),7.44–7.28(m,5H).

[0281] Example 73

[0282] (73)

[0283] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of C⁻¹, and 0.5 mmol of F⁻⁴ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Sodium ethylphenyl(5-phenylthiophen-2-yl)phosphonate was obtained in a yield of 66% (1.54 g). 1 H NMR (400MHz, CDCl3) δ7.94–7.86(m,2H),7.63–7.51(m,4H),7.51–7.44(m,2H),7. 42–7.36(m,2H),7.35–7.30(m,2H),4.19(p,J=7.4Hz,2H),1.40(t,J=7.1Hz,3H).

[0284] Example 74

[0285] (74)

[0286] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of C₂⁻, and 0.5 mmol of F⁻⁴ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, column chromatography was performed to obtain diethyl (5-phenylthiophene-2-yl)phosphonate in a yield of 45%. 1 HNMR (400MHz, CDCl3) δ7.68–7.58(m,3H),7.45–7.39(m,2H),7.38–7.32(m,2H),4.29–4.08(m,4H),1.36(t,J=7.1Hz,6H).

[0287] Example 75

[0288] (75)

[0289] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻⁵ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. 1-(5-(diphenylphosphoyl)thiophen-2-yl)ethane-1-one was obtained in 62% yield. 1 HNMR (400MHz, CDCl3) δ7.79–7.68(m,5H),7.63–7.54(m,3H),7.54–7.46(m,4H),2.58(s,3H).

[0290] Example 76

[0291] (76)

[0292] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻⁶ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. (5-Ethylfuran-2-yl)diphenylphosphine oxide was obtained in a yield of 52%. 1H NMR (400MHz, CDCl3) δ7.87–7.67(m,4H),7.63–7.40(m,6H),6.85(s,1H),6.11(s,1H),2.69(q,J=7.1Hz,2H),1.22(t,J=7.4Hz,3H).

[0293] Example 77

[0294] (77)

[0295] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻⁷ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[b]thiophene-2-yldiphenylphosphine oxide was obtained in a yield of 46%. 1 H NMR (400MHz, CDCl3) δ7.90–7.70(m,7H),7.65–7.55(m,2H),7.53–7.46(m,4H),7.45–7.34(m,2H).

[0296] Example 78

[0297] (78)

[0298] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻⁸ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzo[d]thiazol-2-yldiphenylphosphine oxide was obtained in a yield of 45%. 1 H NMR (400MHz, CDCl3) δ8.20 (d, J = 8.1Hz, 1H), 8.06–7.90 (m, 5H), 7.66–7.54 (m, 3H), 7.54–7.44 (m, 5H).

[0299] Example 79

[0300] (79)

[0301] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻⁹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Benzofuran-2-yldiphenylphosphine oxide was obtained in a yield of 64%. 1 HNMR (400MHz, CDCl3) δ7.85–7.78(m,4H),7.66(d,J=7.7Hz,1H),7.62–7.55(m,2H),7.55–7.47(m,5H),7.44–7.36(m,2H),7.32–7.27(m,1H).

[0302] Example 80

[0303] (80)

[0304] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻¹⁰ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. Methyl 3-(diphenylphospho)-1-hydro-indole-2-carboxylic acid was obtained in 69% yield. 1 H NMR(400MHz, CDCl3)δ10.41(s,1H),7.81(dd,J=11.9,7.8Hz,4H),7.55–7.40(m,7 H),7.26–7.20(m,1H),7.14(d,J=7.9Hz,1H),6.97(t,J=7.3Hz,1H),3.30(s,3H).

[0305] Example 81

[0306] (81)

[0307] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻¹¹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under an LED at 450 ± 10 nm for 36 hours. After the reaction was completed, the mixture was separated by chromatographic column chromatography. Ethyl 3-(diphenylphospho)-1-hydro-indole-2-carboxylic acid was obtained in 57% yield. 1H NMR(600MHz,MeOD)δ7.77–7.70(m,4H),7.62–7.54(m,3H),7.54–7.47(m,4H),7. 31–7.24(m,1H),6.97–6.88(m,2H),3.98(q,J=7.1Hz,2H),1.01(t,J=7.1Hz,3H).

[0308] Example 82

[0309] (82)

[0310] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.5 mmol of F⁻¹⁻¹⁻¹ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. 1-(diphenylphosphoyl)isoquinoline-4-carboxynitrile was obtained in 57% yield. 1 H NMR (400MHz, CDCl3) δ9.67(d,J=8.6Hz,1H),8.93(s,1H),8.25(d,J=8.3Hz,1H),7.94(t,J=7.6Hz,1H),7.91–7.76(m,5H),7.64–7.38(m,6H).

[0311] Example 83 (Scale-up reaction)

[0312] (33)

[0313] Using Co(dmgH)₂pyCl as a photocatalyst, 0.40 mmol of Co(dmgH)₂pyCl photocatalyst, 4.0 mmol of TEA, 6.0 mmol of A⁻¹, and 4.0 mmol of D⁻¹ were added to 70 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 48 hours. After the reaction was complete, 1.02 g of the product was obtained by column chromatography. Benzo[d]thiazol-2-yldiphenylphosphine oxide was given in 74% yield. 1 HNMR (400MHz, CDCl3) δ8.20 (d, J = 8.1Hz, 1H), 8.06–7.90 (m, 5H), 7.66–7.54 (m, 3H), 7.54–7.44 (m, 5H).

[0314] Example 84 (Scale-up reaction)

[0315] (72)

[0316] Using Co(dmgH)₂pyCl as a photocatalyst, 0.50 mmol of Co(dmgH)₂pyCl photocatalyst, 5.0 mmol of TEA, 5.0 mmol of A⁻¹, and 25.0 mmol of F⁻⁴ were added to 70 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 48 hours. After the reaction was complete, 0.86 g of the product was obtained by column chromatography. Diphenyl(5-phenylthiophene-2-yl)phosphine oxide was given in 48% yield. 1 H NMR (400MHz, CDCl3) δ7.85–7.72(m,4H),7.63–7.53(m,4H),7.52–7.44(m,4H),7.44–7.28(m,5H).

[0317] Example 85 (Solar Reaction)

[0318] (34)

[0319] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.15 mmol of D⁻² were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under sunlight for 21 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. 6-Methylbenzo[d]thiazolyl)diphenylphosphine oxide was obtained in 98% yield. 1 HNMR(400MHz, CDCl3) δ8.06(d,J=8.4Hz,1H),7.96(dd,J=12.3,7.7Hz,4H),7.78( s,1H),7.58–7.52(m,2H),7.52–7.43(m,4H),7.34(d,J=8.4Hz,1H),2.49(s,3H).

[0320] Example 86 (Solar Reaction)

[0321] (35)

[0322] Using Co(dmgH)₂pyCl as a photocatalyst, 0.010 mmol of Co(dmgH)₂pyCl photocatalyst, 0.10 mmol of TEA, 0.1 mmol of A⁻¹, and 0.15 mmol of D⁻³ were added to 2 mL of LDCM, and the air was replaced with an Ar atmosphere. The reaction was carried out at room temperature under sunlight for 21 hours. After the reaction was complete, the mixture was separated by chromatographic column chromatography. 6-Methoxybenzo[d]thiazolyl)diphenylphosphine oxide was obtained in 88% yield. 1H NMR(400MHz, CDCl3) δ8.04(d,J=9.0Hz,1H),7.95(dd,J=12.2,7.7Hz,4H),7.59– 7.52(m,2H),7.52–7.44(m,4H),7.40(s,1H),7.14(d,J=9.0Hz,1H),3.87(s,3H).

[0323] Example 87

[0324] (1)

[0325] Using Co(dmgH)₂pyCl as a photocatalyst, 0.015 mmol of Co(dmgH)₂pyCl photocatalyst, 0.3 mmol of A⁻¹, and 0.1 mmol of B⁻¹ were added to 4 mL of LDCM, and the air was replaced with an Ar atmosphere. The mixture was irradiated at room temperature under a 450 ± 10 nm LED for 36 hours. After the reaction was complete, phenanthrene-6-yldiphenylphosphine oxide was obtained in a yield of 27%.

[0326] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A method for photocatalytic synthesis of phosphorylated heterocyclic aromatic hydrocarbons, characterized in that, Includes the following steps: A cobalt catalyst, a phosphorus oxide compound, and a free radical acceptor are added to a solvent to obtain solution A. Solution A is then irradiated with visible light in an inert gas atmosphere to obtain a phosphorylated heterocyclic aromatic compound. The phosphorus oxide compound is selected from compounds shown in Formula I below; I； The free radical acceptor is an isocyanate compound; the isocyanate compound is selected from one of the compounds shown in Formulas II to IV and Compounds 1 to 5 below; wherein R1and R2each independently represent one of an alkoxy group having a carbon number of C1to C 20 , a naphthyl group, a substituted or unsubstituted phenyl group; R1and R2may be the same or different; a substituent is selected from one or more of H, an alkyl group having a carbon number of C1to C 20 , an alkoxy group having a carbon number of C1to C 20 , F, or Cl; R3~R8 each independently represent H, with C1~C6 carbon atoms. 20 The alkyl group has a carbon number of C1~C2. 20 The alkoxy group has a carbon number of C1~C2. 20 One of the following groups: ester group, F, Cl, Br, CN, CH2F, CHF2, CF3, OCF3, OCHF2, or OCH2F; R3 to R8 may be the same or different; R9, R 10 Each independently represents H, and the number of carbon atoms is C1~C. 20 The alkyl group has a carbon number of C1~C2. 20 One of the following: alkoxy group, F, Cl, Br, OCF3, OCHF2, OCH2F, CH2F, CHF2, or CF3; R9 and R 10 They can be the same or different; R 11 ~R 13 Each independently represents H, and the number of carbon atoms is C1~C. 20 The alkyl group has a carbon number of C1~C2. 20 One of the following: alkoxy group, F, Cl, Br; R 11 ~R 13 They can be the same or different; The cobalt catalyst is one or more of the following: Co(dmgH)2pyCl, Co(dmgBF2)2(H2O)2, Co(dmgH)2Cl2, Co(dmgBF2)2(CH3CN)2, Co(dmgBF2)2(CH3CN)(CH3OH), and Co(dmgBF2)2(CH3CN)(H2O).

2. The method according to claim 1, characterized in that, The phosphorus oxide compound is selected from one of the following compounds:

3. The method according to claim 1, characterized in that, Formulas II to IV are selected from one of the following compounds:

4. The method according to claim 1, characterized in that, The solvent is one or more of the following: dichloromethane, 1,4-dioxane, acetone, diethyl ether, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, N,N-dimethylformamide, dimethylacetamide, toluene, chloroform, dimethyl ether, dichloroethane, and water.

5. The method according to claim 1, characterized in that, The solution A also includes an alkaline compound for providing an alkaline environment, wherein the alkaline compound is one or more of K2CO3, Na2CO3, Cs2CO3, K3PO4, K2HPO4, NaOH, TEA, pyridine, 2,6-dimethylpyridine, or 2,4,6-trimethylpyridine.

6. The method according to claim 1, characterized in that, The molar concentration of the cobalt catalyst in solution A is 10. -5 M-1M.

7. The method according to claim 1, characterized in that, The molar concentration of the phosphorus oxide is 0.001M-10M.

8. The method according to claim 1, characterized in that, The molar concentration of the free radical acceptor is 0.001M-10M.

9. The method according to claim 5, characterized in that, The concentration ratio of the phosphorus oxide to the free radical acceptor is 1:0.01-100.

10. The method according to claim 1, characterized in that, The visible light source is selected from sunlight, LED lamps, medium-pressure mercury lamps, high-pressure mercury lamps, or xenon lamps.

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