Method for generating aryl phenol compound by hydroxylation of aryl fluorine compound through uranium photocatalysis and application of aryl phenol compound

Abstract

The invention discloses a method for generating an aryl phenol compound by hydroxylation of an aryl fluorine compound through uranium photocatalysis. According to the method, a photosensitizer is excited by visible light. All the systems are carried out in an air atmosphere, the formula (1) is used as a reaction raw material, C (sp2)-F bonds of aryl groups are broken in a light environment and a solvent under the auxiliary action of a catalyst and acid, and then hydroxylation is carried out to obtain the aryl phenol compound shown in the formula (2). Defluorination hydration is expected to be realized through hydrogen bond activation of fluorine and fusion of ligands connected in series with uranium to metal charge transfer (LMCT), single electron transfer (SET), hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) processes. The reaction is catalyzed at room temperature, the raw materials are cheap and easy to obtain, the reaction operation is simple, the compatibility of substrate functional groups is good, and the regioselectivity is good. According to the fluid reaction disclosed by the invention, not only can the amplification of aryl fluorine compound basic chemicals be realized, but also the amplification of fine chemicals can be realized. The method has wide application prospect and practical value.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and relates to a method and application for the hydroxylation of aryl fluoride compounds to produce arylphenol compounds by uranium photocatalysis. Background Art

[0002] Aryl fluoride compounds are a very important class of compounds, which are widely used in industries such as medicine, refrigeration, plastics, rubber, smelting, pesticides, etc. 20 - 30% of global pharmaceuticals and 30% of pesticide molecules contain at least one fluorine atom. Many varieties of fluoroplastics, fluororubbers, and fluorocoatings are high-end materials with excellent properties such as high temperature resistance, cold resistance, acid and alkali resistance, etc., and are widely used under extreme conditions. Since fluorine is the element with the highest electronegativity, the covalent bond formed when bonding with carbon atoms is extremely strong, making the C-F bond not easily broken, and its bond dissociation energy (~126 kcal / mol). Therefore, the sustainable degradation of fluorine-containing compounds has become a huge challenge, leading to their accumulation in the environment and the delay of their regeneration ability. In order to promote fluorine chemistry, scientists have now conducted a large number of studies on the activation and transformation of C-F bonds. However, there are certain deficiencies in their activation methods, such as the need for excessive transition metal catalysts, strong bases, high temperatures (above 120 °C), pre-functionalization of fluorine-containing substrates (strong electron-withdrawing groups), etc.

[0003] Therefore, considering the practicality of the actual application of this reaction, it is particularly important to find a method for the activation and cleavage of aryl fluoride compounds that is mild in conditions, environmentally friendly, and easy to operate to prepare arylphenol compounds. Summary of the Invention

[0004] In order to solve the deficiencies of the existing technology, the purpose of the present invention is to provide a method for the hydroxylation of aryl fluoride compounds to produce arylphenol compounds by uranium photocatalysis, which involves C(sp 2 )-F cleavage and C(sp 2 )-O formation. Using aryl fluoride compounds as raw materials and water or organic solvents as solvents, the organic solvents include any one or several of acetic acid, acetonitrile, hexafluoroisopropanol, etc.; preferably, water is used as the solvent, and under the promotion of an acid, a photocatalyst (specifically a uranium-containing photocatalyst, such as uranyl photosensitizer) is catalytically excited by visible light. The aryl fluoride compounds of the present invention can be aryl fluoride compounds at different sites, including those with electron-donating groups or electron-withdrawing groups at the para-position, ortho-position, or meta-position, or aryl fluoride compounds of benzheterocycles and complex fluorine-containing drug molecule intermediates.

[0005] The present invention is expected to achieve: 1) realizing the conversion of aryl fluoride to phenol by photoinduction for the first time; 2) being compatible with electron-rich and neutral aryl fluoride substrates; 3) when water is used as the solvent, water serves as both a hydroxyl source and a solvent; 4) reacting under normal temperature and pressure; 5) post-modification functionalization of drug molecules.

[0006] The reaction conditions of the present invention are mild, the reaction yield is good, and the compatibility of substrate functional groups is high. The fluid reaction of the present invention can not only achieve the transformation of simple aryl fluoride substrates, but also has good regioselectivity. For example, tyrosine kinase inhibitors for non-small cell lung cancer, drugs for treating hypercholesterolemia, lipid-lowering drugs for treating hyperlipidemia, etc. can all be successfully transformed. The present invention has broad application prospects and usage values, providing a simple, efficient, and green synthesis method for the activation of carbon-fluorine bonds in aryl fluoride compounds to generate aryl phenolic compounds. At the same time, it also provides a feasible strategy for the hydroxylation of fluorine-containing compounds with different substituted functional groups and the modification of aryl phenolic drugs, natural products, active molecules, etc.

[0007] The present invention provides a method for the hydroxylation of aryl fluoride compounds to generate aryl phenolic compounds by uranium photocatalysis, which involves the cleavage of C(sp 2 )-F and the formation of C(sp 2 )-O. The method uses the aryl fluoride compound shown in formula (1) as the reaction raw material, and under the illumination environment and solvent, with the action of a catalyst and acid assistance, the aryl phenolic compound shown in formula (2) is obtained through reaction. The reaction process is shown in reaction formula (a);

[0008]

[0009] Among them, Ar is selected from a benzene ring, a benzene ring with substituents, a naphthalene ring, a benzheterocycle, a biphenyl ring, etc.; the substituents include one or several of C1-C5 alkyl, C1-C5 alkoxy, halogen, acyl, cyano, nitro, hydroxyl, free carboxylic acid, free amino, aromatic heterocycle, and / or polycycle, etc.

[0010] Preferably,

[0011] Ar is selected from one or several of phenyl, p-acetylphenyl, p-nitrophenyl, p-methylsulfonylphenyl, p-tert-butylphenyl, p-methoxyphenyl, p-fluorophenyl, p-methoxyphenyl, p-cyanophenyl, p-formate phenyl, m-formate phenyl, m-cyanophenyl, p-methoxyphenyl, o-cyanophenyl, o-acetylphenyl, o-methoxycarbonylphenyl, substituted indolylphenyl, amino acid derivatives, etc.;

[0012] In the present invention, after the reaction is completed, it also includes steps such as extraction, separation, silica gel rotary evaporation, column chromatography separation, etc.

[0013] Specifically, in the present invention, using aryl fluoride compound (1) as the reaction raw material, under normal temperature and pressure atmosphere, in a solvent, under visible light excitation conditions, with the assistance of a catalyst and an acid, the C(sp 2 )-F bond is cleaved to form C(sp 2)-O bond to obtain arylphenol compounds (2).

[0014] In the present invention, the solvent is water or an organic solvent, and the organic solvent includes any one or more of acetic acid, acetonitrile, and hexafluoroisopropanol; preferably, the solvent is water.

[0015] In the present invention, the amount of the solvent used is 2 - 45 mL; preferably, it is 2 mL.

[0016] When the solvent is water, the molar ratio of the aryl fluoride compound to water is 1:5 to 1:10; preferably, it is 1:10.

[0017] In the present invention, the concentration of the aryl fluoride compound in the solvent is 0.02 - 0.2 mol / L; preferably, it is 0.2 mol / L.

[0018] In the present invention, the catalyst is a photocatalyst, selected from any one or more of uranyl acetate, uranyl nitrate, uranyl zinc acetate, uranyl sulfate, uranium carbonate, uranyl chloride, etc.; the amount of the catalyst used is 2 - 8 mol% of the aryl fluoride compound shown in formula (1); preferably, the amount of the catalyst used is 8 mol%.

[0019] In the present invention, the acid is a Lewis acid, selected from any one or more of sulfuric acid, formic acid, acetic acid, hydrochloric acid, methanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, hydrobromic acid, trifluoromethanesulfonic acid, phosphoric acid, ferric trichloride, zinc chloride, etc.; the molar amount of the acid used is 4 - 10 equivalents of the aryl fluoride compound shown in formula (1); preferably, the molar amount of the acid used is 10 equivalents of the aryl fluoride compound shown in formula (1).

[0020] In the present invention, the light source used in the light irradiation environment is a blue light source with a wavelength of 430 - 460 nm and a power of 1 - 100 W.

[0021] In a specific embodiment, in a small-scale reaction (0.2 mmol), the light source is a mild blue visible light, and the light source can be a 1 - 6 W blue LED lamp (wavelength 460 nm) or a 1 - 6 W blue LED lamp (wavelength 430 nm); preferably, the light source is a 6 W blue LED lamp (wavelength 460 nm).

[0022] In another specific embodiment, in a fluid reaction (10 mmol), the light source is a mild blue visible light, and the light source can be a 1 - 100 W blue LED lamp (wavelength 460 nm) or the light source is a 1 - 100 W blue LED lamp (wavelength 430 nm); preferably, the light source is an 80 W blue LED lamp (wavelength 460 nm).

[0023] In the present invention, the reaction temperature is 0 - 40 °C; preferably, it is carried out at room temperature of 25 °C.

[0024] In the present invention, the reaction time is 1 - 3 days; preferably, the reaction time is 2 days.

[0025] In the present invention, the reaction is continuously irradiated with light until the reaction ends, that is, the light irradiation time is 1 - 3 days. Preferably, the light irradiation time is 2 days.

[0026] In the present invention, the reaction is preferably carried out at room temperature and normal pressure.

[0027] The present invention also provides arylphenol compounds obtained by the above synthesis method, including:

[0028]

[0029]

[0030] The present invention also provides an application of the above method in hydrolysis of aryl fluoride compounds, hydroxylation of aryl fluoride compounds, defluorination hydration of aryl fluoride compounds, synthesis of arylphenol compounds, preparation of arylphenol drugs, transformation of arylphenol drugs, etc.

[0031] In a specific example of the conversion of aryl fluoride compounds shown in formula (1) on a small scale (0.2 mmol), in the present invention, the synthesis reaction is carried out in reaction flask A. Add aryl fluoride compound (0.2 mmol), photocatalyst uranyl acetate (0.016 mmol), sulfuric acid (2 mmol), and water (2 mL), and stir at room temperature of 25 °C under visible light (blue LED lamp, 460 nm, 6 W) irradiation for 48 hours; after the reaction is completed, extract with diethyl ether, wash with sodium chloride aqueous solution, dry with anhydrous sodium sulfate, evaporate to dryness, add organic solvent (DCM / EA) and silica gel and evaporate to dryness again, and separate by column chromatography to obtain the arylphenol compound shown in formula (2).

[0032] The beneficial effects of the present invention include: a) Visible light catalyzes the reaction at room temperature, which is green, environmentally friendly and easy to operate; b) It has wide universality, relatively high reaction yield and high functional group tolerance; c) The synthesis method can not only achieve the hydroxylation conversion of various aryl fluoride compounds on a small scale; d) It has good regioselectivity; e) It has high potential drug value. For example, ezetimibe is a lipid-lowering drug for treating patients with hyperlipidemia, and its intermediate can be respectively transformed into phenols; atorvastatin is a drug for treating high blood cholesterol, and its industrial intermediate can also be successfully transformed; the advanced intermediate of afatinib is a tyrosine kinase inhibitor, which is widely used in non-small cell lung cancer, etc.; the above intermediates can all be successfully transformed. The method of the present invention provides a new strategy for the conversion of aryl fluoride compounds.

[0033] Mechanism verification method

[0034]

[0035] In the present invention, the mechanism exploration conditions are selected from H 2 18 O and H 2 16 O for exploration; firstly, preferably, the conditional solvent is selected as H 2 18 O to replace H 2 16 O, and the dosage is 2 mL.

[0036] In the present invention, the mechanism exploration conditions are selected from 16 O 2 and 18 O 2 for exploration: firstly, preferably, the conditional gas atmosphere is selected as 18 O 2 to replace 16 O 2 .

[0037] In the present invention, the mechanism exploration conditions are selected from using GC-MS or LC-MS for product identification; firstly, preferably, the identification means and conditions are GC-MS.

[0038] In the present invention, the mechanism exploration conditions are selected from using high-resolution mass spectrometry or low-resolution mass spectrometry for product characterization; firstly, preferably, the product characterization means is high-resolution mass spectrometry.

[0039] Peroxouranium crystal cultivation

[0040]

[0041] In the present invention, the mechanism exploration conditions are as follows: Burns and his colleagues reported a method for generating uranyl peroxide complexes and molecular hydrogen from uranyl nitrate in a pyridine medium. Uranium peroxide-bridged single crystals were cultivated by this method. Preferably, after obtaining the single crystal, the photosensitivity was firstly explored. The photosensitizer has no ultraviolet fluorescence absorption, so it has no photosensitizer characteristics.

[0042] In the present invention, the mechanism exploration conditions are preferably, after obtaining the single crystal, the experimental studies shown in (a), (b), and (c) above are carried out, and the results are as expected. Detailed implementation manners

[0043] Combined with the following specific embodiments, the present invention will be further described in detail. The processes, conditions, experimental methods, etc. for implementing the present invention, except for the specifically mentioned content below, are all common knowledge and well-known common sense in the art, and the present invention has no particularly restricted content.

[0044] The synthesis reaction of the arylphenol compound of the present invention comprises the following steps: In reaction flask A, add aryl fluoride compound (1), uranyl acetate as the photocatalyst, sulfuric acid, and water (2 mL), and stir at normal temperature and pressure under visible light irradiation; after the reaction is completed, extract with diethyl ether, wash with sodium chloride, dry with anhydrous sodium sulfate, add silica gel and spin-dry, spin-dry again, add organic solvent (DCM / EA) and silica gel and spin-dry again, and obtain the arylphenol compound (2) through column chromatography separation;

[0045] Or in reaction flask A, add aryl fluoride compound (1), uranyl acetate as the photocatalyst, acetic acid (2 mL), and stir at normal temperature and pressure under visible light irradiation; after the reaction is completed, extract with diethyl ether, wash with sodium chloride, dry with anhydrous sodium sulfate, add silica gel and spin-dry, spin-dry again, add organic solvent (DCM / EA) and silica gel and spin-dry again, and obtain the arylphenol compound (2) through column chromatography separation;

[0046] Or, in reaction flask A, add aryl fluoride compound (1), water, uranyl acetate as the photocatalyst, acetic acid, and hexafluoroisopropanol (2 mL), and stir at normal temperature and pressure under visible light irradiation; after the reaction is completed, extract with diethyl ether, wash with sodium chloride, dry with anhydrous sodium sulfate, add silica gel and spin-dry, spin-dry again, add organic solvent (DCM / EA) and silica gel and spin-dry again, and obtain the arylphenol compound (2) through column chromatography separation.

[0047] The present invention can achieve the technical effect of hydroxylating the aryl fluoride compound (1) to generate the arylphenol compound (2) within the temperature range of 0 - 40 °C, preferably within the room temperature range.

[0048] Example 1

[0049]

[0050] In a 25 mL Schlenk tube, add p-fluoroacetophenone (0.2 mmol, 27.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), 2N H 2 SO 4 (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 hours. After monitoring the reaction by TLC and completion, extract with diethyl ether or ethyl acetate, and after concentration, obtain the white solid 2a (23.9 mg, 94%) through column chromatography (V PE / V EA = 10 / 1). M.p. 121.5 - 122.3 °C; 1 H NMR (400 MHz, CDCl 3) δ 7.91 (d, J = 8.7 Hz, 2H), 6.95 (d, J = 8.7 Hz, 2H), 2.58 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 198.9, 161.9, 131.5, 129.7, 115.8, 26.4. IR (neat, cm -1 ) 3178, 2358, 1645, 1598, 1435, 1361, 1166, 946, 835, 570. HRMS (ESI) [M+H] + Calculated for 137.0593, Found 137.0595.

[0051] Fluid amplification chemistry: In a 100 mL three-necked flask, add 4-fluoroacetophenone 1a (2.76 g, 20 mmol), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 1.6 mmol, 678 mg), add deionized water (30 mL), acetonitrile (15 mL), and stir under an air atmosphere. Under the action of a peristaltic pump, the liquid is circulated in a polytetrafluoroethylene tube (O.D. = 2 mm, I.D. = 1 mm, length = 11.36 m, volume = 8.9 mL) (flow rate 0.5 mL / min), and at the same time, a blue LED light (460 nm, 80 W) irradiates the polytetrafluoroethylene tube. React at room temperature for 51 hours. After the reaction is completed, extract, concentrate, and obtain white solid 2a (2.42 g, 89%) by column chromatography (V PE / V EA = 10 / 1), and the reaction efficiency is 0.35 mmol / h.

[0052] Example 2

[0053]

[0054] In a 25 mL Schlenk tube, add 4'-fluoropropiophenone (0.2 mmol, 30.8 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under an air atmosphere with a blue LED (460 nm, 6 W) for 48 hours. After monitoring the reaction by TLC and completion, extract with ether or ethyl acetate, concentrate, and then by column chromatography (V PE / V EA=(5 / 1) to obtain a pale yellow solid 2b (17.4 mg, 60%). M.p. 152.3─153.4 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 10.32 (brs, 1H), 7.83 (d, J = 8.6 Hz, 2H), 6.84 (d, J = 8.6 Hz, 2H), 2.90 (q, J = 7.2 Hz, 2H), 1.04 (t, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 198.9, 162.3, 130.7, 128.7, 115.6, 31.0, 8.8. IR (neat, cm -1 ) 3726, 3215, 2922, 2341, 1573, 1236, 1171, 800, 699. HRMS (ESI) [M+H] + Calculated for C 9 H 11 O 2 151.0754, Found 151.0753.

[0055] Example 3

[0056]

[0057] In a 25 mL Schlenk tube, add p-fluorobenzoic acid (0.2 mmol, 28 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 hours. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then by column chromatography (V PE / V E A / V DCM = 3 / 1 / 1) to obtain a white solid 2c (18.5 mg, 68%). M.p. 199.3─200.7 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 12.41 (s, 1H), 10.21 (brs, 1H), 7.79 (d, J = 8.3 Hz, 2H), 6.82 (d, J = 8.4 Hz, 2H). 13 C NMR (101 MHz, DMSO-d 6) δ 167.6, 162.1, 132.0, 121.8, 115.6. IR (neat, cm -1 ) 3345, 3206, 2974, 2457, 1666, 1276, 1109, 989, 733. HRMS (ESI) [M+H] + Calculated for C 7 H 7 O 3 139.0390, Found 139.0388.

[0058] Fluid amplification chemistry: In a 100 mL three-necked flask, add 4-fluorobenzoic acid 1c (2.8 g, 20 mmol), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 1.6 mmol, 678 mg), add deionized water (30 mL), acetonitrile (15 mL), and stir under an air atmosphere. Under the action of a peristaltic pump, the liquid is circulated in a polytetrafluoroethylene tube (O.D. = 2 mm, I.D. = 1 mm, length = 11.36 m, volume = 8.9 mL) (flow rate 0.5 mL / min), and at the same time, a blue LED light (460 nm, 80 W) irradiates the polytetrafluoroethylene tube. React at room temperature for 37 hours. After the reaction is completed, extract, concentrate, and obtain white solid 2c (1.92 g, 70%) by column chromatography (V PE / V E A / V DCM = 3 / 1 / 1), and the reaction efficiency is 0.38 mmol / h.

[0059] Example 4

[0060]

[0061] In a 25 mL Schlenk tube, add methyl 4-fluorobenzoate (0.2 mmol, 30.8 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under an air atmosphere with a blue LED (460 nm, 6 W) for 48 hours. After monitoring the reaction by TLC and completion, extract with diethyl ether or ethyl acetate, concentrate, and then obtain white solid 2d (18.8 mg, 65%) by column chromatography (V PE / V EA = 20 / 1). M.p. 112.6─123.9 °C;1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.32 (brs, 1H), 7.81 (d, J = 8.3 Hz, 2H), 6.85 (d, J = 8.2 Hz, 2H), 3.78 (s, 3H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 166.5, 162.4, 131.9, 120.76, 115.6, 52.1. IR (neat, cm -1 ) 3245, 2860, 1779, 1471, 1115, 998, 876, 556. HRMS (ESI) [M + H] + Calculated for C 8 H 9 O 3 153.0546, Found 153.0545.

[0062] Example 5

[0063]

[0064] In a 25 mL Schlenk tube, ethyl 4-fluorobenzoate (0.2 mmol, 33.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After completion of the reaction monitored by TLC, the mixture was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 20 / 1) to obtain white solid 2e (10.0 mg, 63%). M.p. 103.2─104.5 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 7.96 (d, J = 8.7 Hz, 2H), 6.90 (d, J = 8.7 Hz, 2H), 4.36 (q, J = 7.1 Hz, 2H), 1.38 (t, J = 7.1 Hz, 3H). 13 13C NMR (101 MHz, CDCl 3 ) δ 167.3, 160.5, 132.0, 122.3, 115.3, 61.1 14.3. IR (neat, cm -1)3215,2360,1678,1591,1369,1240,1168,1016.HRMS(ESI)[M+H] + Calculated for C 9 H 11 O 3 167.0703, Found 167.0700.

[0065] Example 6

[0066]

[0067] In a 25 mL Schlenk tube, add tert-butyl 4-fluorobenzoate (0.2 mmol, 39.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under an air atmosphere with a blue LED (460 nm, 6 W) for 48 hours. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the white solid 2f (32.9 mg, 85%) by column chromatography (V PE / V EA = 10 / 1). M.p. 126.3─127.6 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.89 (d, J = 8.6 Hz, 2H), 7.17 (brs, 1H), 6.88 (d, J = 8.8 Hz, 2H), 1.59 (s, 9H). 13 C NMR (101 MHz, CDCl 3 ) δ 166.6, 160.3, 131.8, 123.8, 115.18, 81.3, 28.3 IR (neat, cm -1 ) 3315, 3240, 2981, 1701, 1593, 1265, 1128, 852, 756. HRMS(ESI)[M+Na] + Calculated for C11H14O3Na 217.0835, Found 217.0832.

[0068] Example 7

[0069]

[0070] In a 25 mL Schlenk tube, add p-cyanofluorobenzene (0.2 mmol, 24.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain a white solid (23.6 mg, 82%) by column chromatography (V PE / V EA = 10 / 1). M.p. 100.7─101.5 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 10.61 (brs, 1H), 7.63 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 8.3 Hz, 2H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 162.0, 134.7, 110.0, 116.8, 101.5. IR (neat, cm -1 ) 3240, 2878, 2570, 2177, 1563, 1244, 804, 677. GCMS (EI) m / z, [M] + = 119. 1

[0071] Flow amplification chemistry: In a 100 mL three-necked flask, add p-fluorobenzonitrile 1 g (2.42 g, 20 mmol), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 1.6 mmol, 678 mg), add deionized water (30 mL), acetonitrile (15 mL), and stir under an air atmosphere. Under the action of a peristaltic pump, the liquid is circulated in a polytetrafluoroethylene tube (O.D. = 2 mm, I.D. = 1 mm, length = 11.36 m, volume = 8.9 mL) (flow rate 0.5 mL / min), and at the same time, irradiate the polytetrafluoroethylene tube with a blue LED lamp (460 nm, 80 W). React at room temperature for 23 h. After the reaction is complete, extract, concentrate, and obtain a white solid (1.9 g, 80%) by column chromatography (V PE / V EA = 10 / 1), and the reaction efficiency is 0.7 mmol / h

[0072] Example 8

[0073]

[0074] In a 25 mL Schlenk tube, p-fluorophenyl sulfone (0.2 mmol, 34.8 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2 N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After monitoring the reaction by TLC until completion, the mixture was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain a white solid 2h (14.5 mg, 84%). M.p. 65.8─66.9 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 7.75 (d, J = 8.8 Hz, 2H), 7.44 (brs, 1H), 6.97 (d, J = 8.8 Hz, 2H), 3.06 (s, 3H). 13 13C NMR (101 MHz, CDCl 3 ) δ 161.3, 131.1, 129.7, 116.3, 44.9. IR (neat, cm -1 ) 3440, 3188, 2927, 2360, 1585, 1374, 1087, 958, 765, 732. HRMS (ESI) [M+H] + Calculated for C 7 H 9 O 3 S 173.0267, Found 173.02678.

[0075] Example 9

[0076]

[0077] In a 25 mL Schlenk tube, p-nitrofluorobenzene (0.2 mmol, 28.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2 N H 2 SO 4(2 mL). Under irradiation with a blue LED (460 nm, 6 W) in an air atmosphere, stir for 48 hours. After monitoring the reaction by TLC and completion of the reaction, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the white solid 2i (18.3 mg, 66%) by column chromatography (V PE / V EA = 10 / 1). M.p. 108.6─109.4 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 11.03 (brs, 1H), 8.11 (d, J = 8.7 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 164.3, 140.1, 126.6, 116.2. IR (neat, cm -1 ) 3360, 3078, 2920, 2360, 1612, 1458, 1296, 844. GCMS (EI) m / z, [M] + = 139

[0078] Example 10

[0079]

[0080] In a 25 mL Schlenk tube, add 4-fluorobenzophenone (0.2 mmol, 40.0 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Under irradiation with a blue LED (460 nm, 6 W) in an air atmosphere, stir for 48 hours. After monitoring the reaction by TLC and completion of the reaction, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the white solid 2j (30.4 mg, 76%) by column chromatography (V PE / V EA = 5 / 1). M.p. 121.8─123.3 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 8.39 (brs, 1H), 7.85–7.73 (m, 4H), 7.63–7.55 (m, 1H), 7.53–7.43 (m, 2H), 6.98 (d, J = 8.5 Hz, 2H). 13 13C NMR (101 MHz, CDCl 3) δ 197.6, 161.4, 137.95, 133.4, 132.42, 129.9, 129.3, 128.4, 115.6. IR (neat, cm -1 ) 3238, 2358, 1631, 1600, 1510, 1444, 1230, 1170, 939, 740. HRMS (ESI) [M+Na] + Calculated for 199.0754, Found 199.0755.

[0081] Example 11

[0082]

[0083] In a 25 mL Schlenk tube, 4-fluorophenyl cyclopropyl ketone (0.2 mmol, 32.8 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC was completed, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain a white solid 2k (22 mg, 68%). M.p. 95.8─97.1 °C; 1 H NMR (400 MHz, CDCl 3 ) 1 H NMR (400 MHz, CDCl 3 ) δ 7.96 (d, J = 7.9 Hz, 2H), 6.93 (d, J = 7.8 Hz, 2H), 2.73–2.61 (m, 1H), 1.28–1.20 (m, 2H), 1.11–1.00 (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 201.0, 161.2, 130.8, 130.3, 115.5, 16.9, 11.8. IR (neat, cm -1 ) 3255, 2924, 2357, 1645, 1577, 1388, 1232, 1166, 993, 840, 601. HRMS (ESI) [M+H] + Calculated for C 10 H 11 O 2163.0754, Found 163.0775.

[0084] Example 12

[0085]

[0086] In a 25 mL Schlenk tube, 4-chloro-4'-fluorobenzoylbutane (0.2 mmol, 40.1 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to obtain a gray powder 2l (25 mg, 64%). M.p. 106.2─107.8 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 7.93 (d, J = 8.8 Hz, 1H), 6.90 (d, J = 8.8 Hz, 2H), 6.30 (brs, 1H), 3.67 (t, J = 6.2 Hz, 2H), 3.13 (t, J = 7.0 Hz, 2H), 2.45–1.89 (m, 2H). 13 13C NMR (101 MHz, CDCl 3 ) δ 198.2, 160.5, 130.7, 129.8, 115.5, 44.8, 35.0, 27.0. IR (neat, cm -1 ) 3365, 2924, 2360, 1662, 1588, 1375, 1232, 1174, 997, 669. HRMS (ESI) [M+H] + Calculated for C 10 H 12 O 2 Cl 199.05520, Found 199.0524.

[0087] Example 13

[0088]

[0089] In a 25 mL Schlenk tube, cyclododecyl 4-fluorobenzoate (0.2 mmol, 60.1 mg), UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Under irradiation with a blue LED (460 nm, 6 W) in an air atmosphere, stir for 48 h. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the white solid 2m (52.2 mg, 86%) by column chromatography (V PE / V EA = 30 / 1). M.p. 131.4─133.0 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 7.95 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 5.51 (brs, 1H), 5.26–5.16 (m, 1H), 1.85–1.77 (m, 2H), 1.65–1.61 (m, 2H), 1.48–1.30 (m, 18H). 13 13C NMR (101 MHz, CDCl 3 ) δ 166.1, 159.6, 131.8, 123.6, 115.1, 72.7, 29.2, 24.2, 24.0, 23.4, 23.2, 20.9. IR (neat, cm -1 ) 3348, 2926, 2341, 1676, 1514, 1280, 1165, 850, 773. HRMS (ESI) [M+Na] + Calculated for C 19 H 28 O 3 Na 327.1931, Found 327.1925.

[0090] Example 14

[0091]

[0092] In a 25 mL Schlenk tube, add 3'-fluoroacetophenone (0.2 mmol, 27.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Under irradiation with a blue LED (460 nm, 6 W) in an air atmosphere, stir for 48 h. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the product by column chromatography (V PE / V EA= 5 / 1) gave white solid 2n (15.6 mg, 60%). M.p. 89.6─91.3 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.54 (s, 1H), 7.51 (d, J = 7.7 Hz, 1H), 7.33 (t, J = 7.9 Hz, 1H), 7.11 (d, J = 8.0 Hz, 1H), 2.60 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 199.5, 156.5, 138.3, 129.9, 121.0, 120.9, 114.8, 26.8. IR (neat, cm -1 ) 3360, 3061, 2360, 2239, 1597, 1442, 1282, 995, 867. HRMS (ESI) [M+H] + Calculated for C 8 H 9 O 2 137.0597, Found 137.0597.

[0093] Example 15

[0094]

[0095] In a 25 mL Schlenk tube, 3-fluoropropiophenone (0.2 mmol, 19.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to give white solid 2o (17.2 mg, 56%). M.p. 68.2─69.3 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.63 (d, J = 1.8 Hz, 1H), 7.50 (d, J = 7.7 Hz, 1H), 7.31 (t, J = 7.9 Hz, 1H), 7.13 (dd, J = 8.1, 2.4 Hz, 1H), 3.00 (q, J = 7.2 Hz, 2H), 1.21 (t, J = 7.2 Hz, 3H). 1313C NMR (101 MHz, CDCl 3 ) δ 202.8, 156.6, 137.9, 129.9, 120.9, 120.5, 114.7, 32.1, 8.3. IR (neat, cm -1 ) 3294, 2941, 1957, 1567, 1465, 1269, 1078, 995, 871, 786. HRMS (ESI) [M+H] + Calculated for C 9 H 11 O 2 151.0754, Found 151.0753.

[0096] Example 16

[0097]

[0098] In a 25 mL Schlenk tube, add m-fluorobenzoic acid (0.2 mmol, 28 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 hours. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain white powder 2p (16.5 mg, 62%) by column chromatography (V PE / V EA / V DCM = 5 / 1 / 1). M.p. 195.6─197.3 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 12.80 (brs, 1H), 9.74 (brs, 1H), 7.38 (d, J = 7.6 Hz, 1H), 7.34 (s, 1H), 7.28 (t, J = 7.8 Hz, 1H), 6.99 (d, J = 8.1 Hz, 1H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 167.7, 157.8, 132.5, 130.1, 120.5, 120.3, 116.2. IR (neat, cm -1 ) 3280, 2360, 1716, 1600, 1487, 1246, 921, 734. HRMS (ESI) [M+H] + Calculated for C7 H 7 O 3 139.0390, Found 139.0389.

[0099] Example 17

[0100]

[0101] In a 25 mL Schlenk tube, methyl 3-fluorobenzoate (0.2 mmol, 30.8 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 hours. After monitoring the reaction by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 20 / 1) to obtain a white solid 2q (15.7 mg, 51%). M.p. 63.6─65.2 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 7.40–7.35 (m, 2H), 7.29 (t, J = 7.8 Hz, 1H), 7.03 (d, J = 8.1 Hz, 1H), 3.80 (s, 3H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 166.7, 158.0, 131.30, 130.2, 120.7, 120.3, 116.1, 52.5. IR (neat, cm -1 ) 3381, 2953, 2360, 1589, 1196, 999, 680. HRMS (ESI) [M+H] + Calculated for C 8 H 9 O 3 153.0546, Found 153.0544.

[0102] Example 18

[0103]

[0104] In a 25 mL Schlenk tube, ethyl 3-fluorobenzoate (0.2 mmol, 33.6 mg), UO 2 (OAc) 2 ·2H2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, extracted with ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 5 / 1) to give a white solid 2r (17.9 mg, 54%). M.p. 65.2─66.3 °C; 1 H NMR (400 MHz, CDCl 3 ) 1 HNMR (400 MHz, CDCl 3 ) δ 7.66–7.57 (m, 2H), 7.31 (t, J = 7.9 Hz, 1H), 7.08 (d, J = 7.9 Hz, 1H), 6.22 (brs, 1H), 4.38 (q, J = 7.1 Hz, 2H), 1.39 (t, J = 7.1 Hz, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 167.0, 155.9, 131.6, 129.7, 121.8, 120.3, 116.4, 61.4, 14.3. IR (neat, cm -1 ) 3381, 2983, 2358, 1685, 1587, 1450, 1286, 1101, 810, 671. HRMS (ESI) [M+H] + Calculated for C 9 H 11 O 3 167.0703, Found 167.0703.

[0105] Example 19

[0106]

[0107] In a 25 mL Schlenk tube, add 3-fluorobenzonitrile (0.2 mmol, 24.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, extracted with ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 10 / 1) gave white powder 2s (16.6 mg, 70%). M.p. 64.4─65.7 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 10.20 (brs, 1H), 7.38 (t, J = 7.8 Hz, 1H), 7.23 (d, J = 7.5 Hz, 1H), 7.14–7.08 (m, 2H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 158.3, 131.4, 123.3, 121.2, 119.3, 118.7, 112.5. IR (neat, cm -1 ) 3340, 2360, 2237, 1612, 1276, 868, 678. HRMS (ESI) [M+H] + Calculated for C 7 H 6 ON 110.0444, Found 110.0445.

[0108] Example 20

[0109]

[0110] In a 25 mL Schlenk tube, 2'-fluoroacetophenone (0.2 mmol, 27.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to give white solid 2t (20.6 mg, 57%). M.p. 97.33─98.9 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 12.28 (brs, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.49 (t, J = 7.8 Hz, 1H), 6.99 (d, J = 8.4 Hz, 1H), 6.92 (t, J = 7.6 Hz, 1H), 2.65 (s, 3H). 13 C NMR (101 MHz, CDCl 3) δ 204.5, 162.4, 136.4, 130.7, 119, 118.9, 118.4, 26.6. IR (neat, cm -1 ) 3172, 2360, 1660, 1575, 1489, 1294, 1217, 960, 791. HRMS (ESI) [M+H] + Calculated for 137.0596, Found 137.0598.

[0111] Example 21

[0112]

[0113] In a 25 mL Schlenk tube, add 2-fluorobenzonitrile (0.2 mmol, 24.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 hours. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain a pale yellow crystal 2u (13.8 mg, 62%) by column chromatography (V PE / V EA = 15 / 1). M.p. 78.6 - 79.9 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 11.04 (brs, 1H), 7.59 (d, J = 7.7 Hz, 1H), 7.49 (t, J = 7.9 Hz, 1H), 7.02 (d, J = 8.4 Hz, 1H), 6.93 (t, J = 7.5 Hz, 1H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 160.6, 135.2, 133.7, 110.0, 117.5, 116.6, 99.3. IR (neat, cm -1 ) 3275, 2227, 1602, 1502, 1454, 1303, 1159, 1099, 846, 746. HRMS (ESI) [M+H] + Calculated for C 7 H 6 ON 110.0444, Found 110.0446.

[0114] Example 22

[0115]

[0116] In a 25 mL Schlenk tube, add fluorobenzene (0.2 mmol, 19.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the white liquid 2v (10.7 mg, 57%) by column chromatography (V PE / V EA = 15 / 1). 1 1H NMR (400 MHz, CDCl 3 ) δ 7.35–7.28 (m, 2H), 7.03 (t, J = 7.4 Hz, 1H), 6.95 (d, J = 7.7 Hz, 2H). 13 13C NMR (101 MHz, CDCl 3 ) δ 155.2, 129.9, 121.2, 115.6. IR (neat, cm -1 ) 3226, 3215, 3208, 3094, 3047, 2966, 1547, 992. HRMS (ESI) [M+H] + Calculated for C 6 H 7 O 95.0491, Found 95.0496.

[0117] Flow chemistry: In a 100 mL three-necked flask, add fluorobenzene 1v (9.6 g, 100 mmol), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 8 mmol, 3.4 g), add deionized water (30 mL), acetonitrile (15 mL) and stir in an air atmosphere. Under the action of a peristaltic pump, the liquid is circulated in a PTFE tube (O.D. = 2 mm, I.D. = 1 mm, length = 11.36 m, volume = 8.9 mL) (flow rate 0.5 mL / min), while irradiating the PTFE tube with a blue LED lamp (460 nm, 80 W), react at room temperature for 14 h. After the reaction is complete, extract, concentrate, and by column chromatography (V PE / V EA= 20 / 1) to obtain a light yellow liquid 2v (4.45 g, 47%), and the reaction efficiency was 3.36 mmol / h.

[0118] Example 23

[0119]

[0120] In a 25 mL Schlenk tube, 4-fluorobiphenyl (0.2 mmol, 34.4 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 hours. After monitoring the completion of the reaction by TLC, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain a white powder 2w (17.7 mg, 52%). M.p. 154.8 - 155.6 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 9.58 (brs, 1H), 7.56 (d, J = 7.8 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 7.40 (t, J = 7.6 Hz, 2H), 7.26 (t, J = 7.3 Hz, 1H), 6.87 (d, J = 8.3 Hz, 2H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 162.4, 145.4, 136.2, 134.0, 132.9, 131.6, 131.2, 121.0. IR (neat, cm -1 ) 3404, 2360, 1608, 1423, 1228, 1004, 711. GCMS (EI) m / z, [M] + = 170. 1

[0121] Example 24

[0122]

[0123] In a 25 mL Schlenk tube, N-(4-fluorophenyl)-4-methylbenzenesulfonamide (0.2 mmol, 56.6 mg), UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, extraction was carried out with diethyl ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 5 / 1) to obtain a gray powder 2x (28.5 mg, 53%). M.p. 126.6─127.4 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 9.64 (brs, 1H), 9.28 (brs, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 6.83 (d, J = 8.5 Hz, 2H), 6.59 (d, J = 8.5 Hz, 2H), 2.33 (s, 3H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 155.1, 143.31, 137.1, 129.93, 129.1, 127.2, 124.4, 115.9, 21.4. IR (neat, cm -1 ) 3350, 3238, 2360, 1597, 1510, 1328, 1123, 1089, 906, 796. HRMS (ESI) [M+Na] + Calculated for C 13 H 14 O 3 NS 264.0689, Found 264.0688.

[0124] Example 25

[0125]

[0126] In a 25 mL Schlenk tube, 4-fluoroacetanilide (0.2 mmol, 30.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, extraction was carried out with diethyl ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 2 / 1) to obtain a white powder 2y (20.5 mg, 68%). M.p. 160.3─161.8 °C;1 1H NMR (400 MHz, DMSO-d 6 ) δ 9.66 (s, 1H), 9.16 (s, 1H), 7.35 (d, J = 8.8 Hz, 2H), 6.69 (d, J = 8.8 Hz, 2H), 1.99 (s, 3H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 168.1, 153.6, 131.55, 121.4, 115.5, 24.2. IR (neat, cm -1 ) 3251, 2954, 2358, 1668, 1549, 1458, 1242, 1109, 837. HRMS (ESI) [M + H] + Calculated for C 8 H 10 O 2 N 152.0706, Found 152.0707.

[0127] Fluid amplification chemistry: In a 100 mL three-necked flask, add 4-fluoroacetanilide 1y (3.06 g, 20 mmol), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 1.6 mmol, 67.8 mg), add deionized water (45 mL), acetonitrile (15 mL), and stir under an air atmosphere. Under the action of a peristaltic pump, the liquid is circulated in a polytetrafluoroethylene tube (O.D. = 2 mm, I.D. = 1 mm, length = 11.36 m, volume = 8.9 mL) (flow rate 0.5 mL / min), and at the same time, a blue LED light (460 nm, 80 W) irradiates the polytetrafluoroethylene tube. React at room temperature for 70 hours. After the reaction is completed, extract, concentrate, and obtain white powder 2y (1.86 g, 61%) by column chromatography (V PE / V EA = 2 / 1), and the reaction efficiency is 0.17 mmol / h

[0128] Example 26

[0129]

[0130] In a 25 mL Schlenk tube, add 4-fluoroanisole (0.2 mmol, 25.2 mg), UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and HFIP (2 mL). The mixture was irradiated and stirred for 48 h under a blue LED (460 nm, 6 W) in air. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to obtain an oily liquid 2z (15.0 mg, 60%). 1 1H NMR (400 MHz, CDCl 3 ) δ 6.89–6.77 (m, 4H), 3.78 (s, 3H). 13 13C NMR (101 MHz, CDCl 3 ) δ 153.5, 149.6, 116.3, 115.2, 56.1. IR (neat, cm -1 ) 3365, 2953, 2360, 1507, 1439, 1213, 1029, 823. HRMS (ESI) [M+H] + Calculated for C 7 H 9 O 2 125.0597, Found 125.0597.

[0131] Example 27

[0132]

[0133] In a 25 mL Schlenk tube, 2-chloro-4'-fluoroacetanilide (0.2 mmol, 37.5 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred for 48 h under a blue LED (460 nm, 6 W) in air. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 3 / 1) to obtain a pale yellow crystal 2aa (25.0 mg, 74%). M.p. 125.7─127.1 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.01 (s, 1H), 9.26 (s, 1H), 7.36 (d, J = 8.1 Hz, 2H), 6.71 (d, J = 8.4 Hz, 2H), 4.18 (s, 2H). 13 13C NMR (101 MHz, DMSO-d 6)δ164.40,154.27,130.52,121.66,115.65,43.98.IR(neat,cm -1 )3392,2920,2341,1647,1516,1217,669.HRMS(ESI)[M+H] + Calculated for C 8 H 9 O 2 NCl186.0316,Found 186.0320.

[0134] Example 28

[0135]

[0136] In a 25 mL Schlenk tube, 2-cyano-4'-fluoroacetanilide (0.2 mmol, 35.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to obtain white solid 2ab (21.4 mg, 61%). M.p. 218.9─200.3 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.04 (s, 1H), 9.29 (s, 1H), 7.32 (d, J = 8.6 Hz, 2H), 6.71 (d, J = 8.8 Hz, 2H), 3.81 (s, 2H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 160.7, 154.3, 130.4, 121.5, 116.6, 115.7, 26.7. IR(neat,cm -1 ) 3726, 2956, 2341, 1558, 1456, 1130, 1083, 750. HRMS(ESI)[M+Na] + Calculated forC 9 H 8 O 2 N 2 Na 199.0478,Found 199.0482.

[0137] Example 29

[0138]

[0139] In a 25 mL Schlenk tube, 2-fluorobiphenyl (0.2 mmol, 34.4 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain a white solid 2ac (25.5 mg, 75%). M.p. 53.6─54.3 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 9.58 (s, 1H), 7.58 (d, J = 7.2 Hz, 2H), 7.40 (t, J = 7.6 Hz, 2H), 7.33–7.25 (m, 2H), 7.18 (t, J = 7.7 Hz, 1H), 7.04–6.98 (m, 1H), 6.90 (t, J = 7.4 Hz, 1H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 154.8, 139.1, 130.8, 129.6, 128.9, 128.3, 126.9, 119.9, 116.5. IR (neat, cm -1 ) 3525, 3446, 3030, 1583, 1433, 1269, 1170, 1008, 827, 698. HRMS (ESI) [M+H] + Calculated for C 12 H 11 O 171.0804, Found 171.1494.

[0140] Example 30

[0141]

[0142] In a 25 mL Schlenk tube, 2-fluoroacetanilide (0.2 mmol, 30.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO4 (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the completion of the reaction by TLC, extraction was carried out with diethyl ether or ethyl acetate, followed by concentration. Then, column chromatography (V PE / V EA = 3 / 1) gave a grayish-brown powder 2ad (15.3 mg, 52%). M.p. 202.8─204.5 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 9.72 (s, 1H), 9.29 (s, 1H), 7.66 (d, J = 7.8 Hz, 1H), 6.93 (t, J = 7.6 Hz, 1H), 6.85 (d, J = 7.9 Hz, 1H), 6.75 (t, J = 7.6 Hz, 1H), 2.09 (s, 3H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 169.5, 148.34, 126.9, 125.1, 122.8, 119.4, 116.5, 24.1. IR (neat, cm -1 ) 3404, 2924, 2358, 1654, 1593, 1400, 1282, 765, 667. HRMS (ESI) [M+H] + Calculated for C 8 H 10 O 2 N 152.0706, Found 152.0707.

[0143] Example 31

[0144]

[0145] In a 25 mL Schlenk tube, 2-fluoroanisole (0.2 mmol, 25.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the completion of the reaction by TLC, extraction was carried out with diethyl ether or ethyl acetate, followed by concentration. Then, column chromatography (V PE / V EA = 10 / 1) gave a colorless liquid 2ae (14.8 mg, 52%). 1 1H NMR (400 MHz, CDCl 3)δ7.06–6.99(m,1H),6.98–6.85(m,3H),5.77(brs,1H),3.89(s,3H). 13 C NMR(101MHz,CDCl 3 )δ146.8,145.8,121.5,120.3,114.8,110.9,55.9.IR(neat,cm -1 )3441,3066,1614,1469,1361,1222,1145,918,760.HRMS(ESI)[M+H] + Calculated for C 7 H 9 O 2 125.0597,Found 125.0598.

[0146] Example 32

[0147]

[0148] In a 25 mL Schlenk tube, 3-bromo-4-fluorobenzamide (0.2 mmol, 43.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After completion of the reaction monitored by TLC, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V DCM / V MeOH = 10 / 1) to obtain white powder crystal 2af (27.1 mg, 63%). M.p. 170.8─171.3 °C; 1 H NMR(400MHz,DMSO-d 6 )δ10.86(s,1H),8.03(d,J = 2.1Hz,1H),7.86(s,1H),7.73(dd,J = 8.5,2.1Hz,1H),7.24(s,1H),6.97(dd,J = 8.5,3.0Hz,1H). 13 C NMR(101MHz,DMSO-d 6 )δ166.8,157.2,132.9,129.0,126.9,116.1,109.3.IR(neat,cm -1)3500,3360,2922,2360,1697,1612,1568,1311,819,781.HRMS(ESI)[M+H] + Calculated for C 7 H 7 O 2 NBr 215.9655,Found 215.9657.

[0149] Example 33

[0150]

[0151] In a 25 mL Schlenk tube, 3-fluoroacetanilide (0.2 mmol, 30.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After monitoring the reaction by TLC was completed, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 3 / 1) to obtain white solid 2ag (17.1 mg, 51%). M.p. 138.3─140.0 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 9.77 (s, 1H), 9.32 (s, 1H), 7.17 (s, 1H), 7.04 (t, J = 8.0 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H), 6.41 (d, J = 8.0 Hz, 1H), 2.00 (s, 3H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 168.6, 157.8, 140.8, 129.7, 110.5, 110.2, 106.5, 24.5. IR (neat, cm -1 ) 3302, 2877, 2360, 1668, 1458, 1377, 1157, 968, 688. HRMS(ESI)[M+H] + Calculated for C 8 H 10 O 2 N 152.0706, Found 152.0707.

[0152] Example 34

[0153]

[0154] In a 25 mL Schlenk tube, 2-(4-fluorophenyl)propionic acid (0.2 mmol, 33.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain a white powder 2ah (19.2 mg, 58%). M.p. 118.6─119.7 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.19 (d, J = 8.5 Hz, 2H), 6.79 (d, J = 8.6 Hz, 2H), 3.68 (q, J = 7.2 Hz, 1H), 1.48 (d, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 179.66, 154.79, 132.08, 128.86, 115.51, 44.30, 18.20. IR (neat, cm -1 ) 3228, 2360, 1699, 1514, 1240, 1163, 1068, 854, 827. HRMS (ESI) [M+Na] + Calculated for C 9 H 10 O 3 Na 189.0522, Found 189.0524.

[0155] Example 35

[0156]

[0157] In a 25 mL Schlenk tube, N-(4-(4-fluorophenoxy)phenyl)-4-methylbenzenesulfonamide (0.2 mmol, 71.5 mg), UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, extraction was carried out with diethyl ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 3 / 1) to obtain a red-brown solid 2ai (37 mg, 75%). M.p. 173.4─175.6 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 7.59 (dd, J = 21.2, 8.3 Hz, 2H), 7.20 (s, 1H), 7.16 (d, J = 8.1 Hz, 2H), 7.04–6.92 (m, 2H), 6.92–6.76 (m, 4H), 6.70 (dd, J = 29.7, 8.9 Hz, 2H), 2.33 (s, 3H). 13 13C NMR (101 MHz, CDCl 3 ) δ 156.6, 154.4, 153.9, 149.7, 143.9), 135.6, 130.5, 129.6, 128.6, 127.3, 125.8, 124.9, 120.9, 118.1, 116.5, 116.1, 21.5. IR (neat, cm -1 ) 3307, 2926, 2360, 1714, 1653, 1444, 1215, 1031, 844, 700. HRMS (ESI) [M+H] + Calculated for C 19 H 18 O 4 NS 356.0951, Found 356.0953.

[0158] Example 36

[0159]

[0160] In a 25 mL Schlenk tube, 4-fluorophenoxy-ethyl bromide (0.2 mmol, 43.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, extraction was carried out with diethyl ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA= 10 / 1) gave white solid 2aj (22.2 mg, 51%). M.p. 90.4─91.2 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 6.82 (d, J = 9.2 Hz, 2H), 6.76 (d, J = 9.2 Hz, 2H), 4.63 (brs, 1H), 4.23 (t, J = 6.3 Hz, 2H), 3.61 (t, J = 6.3 Hz, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 152.3, 150.1, 116.2, 116.1, 68.9, 29.4. IR (neat, cm -1 ) 3390, 2943, 2358, 1739, 1508, 1375, 1103, 1014, 815.

[0161] Example 37

[0162]

[0163] In a 25 mL Schlenk tube, 1-(2-bromoethoxy)-2-fluorobenzene (0.2 mmol, 43.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to give yellow liquid 2ak (21.4 mg, 50%). 1 H NMR (400 MHz, CDCl 3 ) δ 7.00–6.90 (m, 2H), 6.85 (d, J = 7.8 Hz, 2H), 5.76 (s, 1H), 4.36 (t, 2H), 3.67 (t, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 146.3, 145.0, 122.7, 120.3, 115.3, 113.0, 69.1, 29.6. IR (neat, cm -1 ) 3487, 3282, 2922, 2341, 1610, 1500, 1259, 1109, 1012, 744.

[0164] Example 38

[0165]

[0166] In a 25 mL Schlenk tube, (4-fluorobenzoyl)-L-alanine methyl ester (0.2 mmol, 45 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain a transparent liquid 2al (34 mg, 83%). 1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.00 (s, 1H), 8.50 (d, J = 6.8 Hz, 1H), 7.75 (d, J = 8.6 Hz, 2H), 6.80 (d, J = 6.8 Hz, 2H), 4.47–4.37 (m, 1H), 3.63 (s, 3H), 1.38 (d, J = 7.3 Hz, 3H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 173.9, 166.4, 160.6, 129.9, 124.8, 115.1, 52.2, 48.5, 17.2. IR (neat, cm -1 ) 3280, 3116, 2956, 2360, 1517, 1361, 1246, 1111, 997, 775. HRMS (ESI) [M+Na] + Calculated for C 11 H 13 O 4 NNa 246.0737, Found 246.0740.

[0167] Example 39

[0168]

[0169] In a 25 mL Schlenk tube, (4-fluorobenzoyl)-L-valine methyl ester (0.2 mmol, 50.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4(2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC to completion, extract with ether or ethyl acetate, concentrate, and then obtain white liquid 2am (39 mg, 79%) by column chromatography (V PE / V EA = 5 / 1). M.p. 138.3─139.7 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.32 (brs, 1H), 7.83 (d, J = 8.6 Hz, 2H), 6.84 (d, J = 8.6 Hz, 2H), 2.90 (q, J = 7.2 Hz, 3H), 1.04 (t, J = 7.2 Hz, 4H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 198.9, 162.3, 130.7, 128.7, 115.6, 31.0, 8.8 IR (neat, cm -1 ) 3215, 2922, 2341, 1574, 1236, 800, 650. HRMS (ESI) [M+H] + Calculated for C 9 H 11 O 2 151.0754, Found 151.0753.

[0170] Example 40

[0171]

[0172] In a 25 mL Schlenk tube, add 4-fluoro-1-indanone (0.2 mmol, 30.0 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC to completion, extract with ether or ethyl acetate, concentrate, and then obtain gray powder 2an (15.2 mg, 51%) by column chromatography (V PE / V EA = 5 / 1). M.p. 237.6─239.5 °C; 1 1H NMR (400 MHz, DMSO-d 6) δ 9.99 (s, 1H), 7.23 (t, J = 7.6 Hz, 1H), 7.11–7.02 (m, 2H), 2.92 (t, 2H), 2.58 (t, 2H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 207.1, 155.6, 142.3, 138.9, 129.1, 120.3, 113.8, 36.25, 22.8. IR (neat, cm -1 ) 3234, 3201, 2924, 2358, 1714, 1595, 1292, 1056, 950, 789. HRMS (ESI) [M + H] + Calculated for C 9 H 9 O 2 149.0597, Found 149.0599.

[0173] Example 41

[0174]

[0175] In a 25 mL Schlenk tube, 5-fluoro-1-indanone (0.2 mmol, 30.0 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain a gray powder 2ao (15.9 mg, 53%). M.p. 171.6─173.7 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 10.46 (s, 1H), 7.47 (d, J = 8.3 Hz, 1H), 6.84 (s, 1H), 6.79 (d, J = 8.4 Hz, 1H), 2.97 (t, 2H), 2.52 (t, 2H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 204.5, 164.1, 158.7, 129.1), 125.4, 116.2, 112.5, 36.4, 25.7. IR (neat, cm -1)3198,2926,2359,1664,1575,1471,1303,1101,810,669.HRMS(ESI)[M+H] + Calculated for C 9 H 9 O 2 149.0597,Found 149.0600.

[0176] Example 42

[0177]

[0178] In a 25 mL Schlenk tube, 6-fluoroindole (0.2 mmol, 27 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After monitoring the reaction by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to obtain a dark brown powder 2ap (16 mg, 64%). M.p. 119.3─121.6 °C; 1 H NMR (501 MHz, DMSO-d 6 ) δ 10.64 (s, 1H), 8.84 (s, 1H), 7.28 (d, J = 8.4 Hz, 1H), 7.08 (d, J = 3.0 Hz, 1H), 6.74 (s, 1H), 6.52 (d, J = 8.4 Hz, 1H), 6.25 (d, J = 2.7 Hz, 1H). 13 C NMR (126 MHz, DMSO-d 6 ) δ 153.3, 137.4, 123.6, 121.4, 120.7, 109.9, 101.3, 96.9. IR (neat, cm -1 ) 3261, 2360, 2341, 1737, 1608, 1439 1256, 1170, 858, 769. HRMS(ESI)[M+H] + Calculated for C 8 H 8 ON 134.0600, Found 134.0604.

[0179] Example 43

[0180]

[0181] In a 25 mL Schlenk tube, add 5-fluoroindole-2-carboxaldehyde (0.2 mmol, 33 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 hours. After monitoring the reaction by TLC until completion, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the red solid 2aq (19.8 mg, 64%) by column chromatography (V PE / V EA = 3 / 1). M.p. 258.8─259.3 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.74 (s, 1H), 9.55 (s, 1H), 7.00 (d, J = 8.4 Hz, 1H), 6.84 (s, 1H), 6.74 (d, J = 8.4 Hz, 1H). 13 13C NMR (126 MHz, DMSO-d 6 ) δ 184.9, 159.5, 153.2, 143.2, 125.1, 118.2, 113.1, 110.5. IR (neat, cm -1 ) 3294, 2956, 2868, 2358, 1728, 1647, 1490, 1247, 1082, 846. HRMS (ESI) [M+Na] + Calculated for C 8 H 5 O 3 NNa 186.0162, Found 186.0165.

[0182] Example 44

[0183]

[0184] In a 25 mL Schlenk tube, add 5-fluorobenzoxazole-2-thiol (0.2 mmol, 33.8 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 hours. After monitoring the reaction by TLC until completion, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the product by column chromatography (V PE / V EA= 5 / 1) gave a pale yellow oily liquid 2ar (17.4 mg, 52%). 1 H NMR (400 MHz, DMSO-d 6 ) δ 13.60 (s, 1H), 9.71 (s, 1H), 7.29 (d, J = 8.7 Hz, 1H), 6.63 (d, J = 8.8 Hz, 1H), 6.59 (s, 1H). 13 C NMR (101 MHz, DMSO-d 6 ) δ 180.8, 155.7, 142.0, 132.2, 110.9, 97.3. IR (neat, cm -1 ) 3284, 2997, 2850, 2360, 1732, 1456, 1377, 1276, 1136. HRMS (ESI) [M+H] + Calculated for C 7 H 6 O 2 NS 168.0114, Found 168.0115.

[0185] Example 45

[0186]

[0187] In a 25 mL Schlenk tube, 2-bromo-6-fluorobenzothiazole (0.2 mmol, 46.4 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After monitoring the reaction by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to give a white solid 2as (33.5 mg, 73%). M.p. 176.4─178.7 °C; 1 H NMR (400 MHz, CD 3 OD) δ 7.73 (d, J = 8.9 Hz, 1H), 7.27 (s, 1H), 6.98 (d, J = 8.8 Hz, 1H). 13 C NMR (101 MHz, CD 3 OD) δ 156.3, 145.7, 138.4, 134.9, 122.5, 115.9, 105.8. IR (neat, cm -1) 3053,2958,2362,1600,1421,1265,991,902,734. HRMS(ESI) [M+H] + Calculated for C 7 H 5 ONBrS 229.9270, Found 229.9272.

[0188] Example 46

[0189]

[0190] In a 25 mL Schlenk tube, add 3-(4-fluorophenyl)-1H-pyrazole (0.2 mmol, 32.4 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 hours. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain the white solid 2at (23.0 mg, 73%) by column chromatography (V PE / V EA = 5 / 1). M.p. 142.4─143.6 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 12.78 (brs, 1H), 9.47 (s, 1H), 7.57 (d, J = 8.5 Hz, 3H), 6.78 (d, J = 8.5 Hz, 2H), 6.51 (d, J = 2.0 Hz, 1H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 157.5, 126.9, 115.9, 101.4, 79.8, 79.43, 79.1. IR (neat, cm -1 ) 3265, 2924, 2388, 1734, 1608, 1506, 1361, 1091, 850, 699. HRMS(ESI) [M+H] + Calculated for C 9 H 9 ON 2 161.0709, Found 161.0711.

[0191] Example 47

[0192]

[0193] In a 25 mL Schlenk tube, add ethyl 5-amino-1-(4-fluorophenyl)pyrazole-4-carboxylate (0.2 mmol, 50 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Irradiate and stir under a blue LED (460 nm, 6 W) in an air atmosphere for 48 hours. After monitoring the reaction by TLC is complete, extract with diethyl ether or ethyl acetate, concentrate, and then obtain white crystals 2au (39.5 mg, 80%) by column chromatography (V PE / V EA = 3 / 1). M.p. 123.6─124.3 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.09 (brs, 1H), 7.78 (s, 1H), 7.21 (d, J = 8.7 Hz, 2H), 6.77 (d, J = 8.7 Hz, 2H), 5.19 (s, 2H), 4.36–4.25 (m, 2H), 1.36 (t, J = 7.1 Hz, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 164.5, 157.1, 149.3, 140.2, 128.8, 126.4, 116.8, 95.9, 59.8, 14.5. IR (neat, cm -1 ) 3338, 2926, 2358, 1681, 1610, 1257, 1107, 948, 837, 735, 520. HRMS (ESI) [M+H] + Calculated for C 12 H 14 O 3 N 3 248.1030, Found 248.1033.

[0194] Example 48

[0195]

[0196] In a 25 mL Schlenk tube, add 6-fluoroquinoline (0.2 mmol, 29.4 mg), UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), AcOH (), and HFIP (2 mL). Under irradiation with a blue LED (460 nm, 6 W) in an air atmosphere, stir for 48 h. After monitoring the reaction by TLC until completion, extract with diethyl ether or ethyl acetate, concentrate, and then obtain a dark brown powder 2av (25.5 mg, 75%) by column chromatography (V PE / V EA = 5 / 1). M.p. 168.6─170.4 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 9.97 (brs, 1H), 8.70–8.59 (m, 1H), 8.12 (d, J = 7.7 Hz, 1H), 7.86 (d, J = 8.9 Hz, 1H), 7.38 (d, J = 3.9 Hz, 1H), 7.31 (d, J = 8.7 Hz, 1H), 7.14 (s, 1H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 155.9, 147.6, 143.5, 134.6, 130.9, 129.8, 122.4, 121.8, 108.8. IR (neat, cm -1 ) 3736, 2924, 2341, 1490, 1228, 1091, 926, 711, 669. HRMS (ESI) [M+H] + Calculated for C 9 H 8 ON 146.0600, Found 146.0603.

[0197] Example 49

[0198]

[0199] In a 25 mL Schlenk tube, add 4-fluoro-4'-(trans-4-propylcyclohexyl)-1,1'-biphenyl (0.2 mmol, 59.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Under irradiation with a blue LED (460 nm, 6 W) in an air atmosphere, stir for 48 h. After monitoring the reaction by TLC until completion, extract with diethyl ether or ethyl acetate, concentrate, and then obtain a white powder 2aw (30.3 mg, 51%) by column chromatography (V PE / V EA = 5 / 1). M.p. 98.8─100.2 °C; 11H NMR (400 MHz, CDCl 3 ) δ 7.50–7.43 (m, 4H), 7.28–7.25 (m, 2H), 6.89 (d, J = 8.5 Hz, 2H), 4.80 (brs, 1H), 2.49 (t, J = 12.1 Hz, 1H), 1.90 (t, J = 14.7 Hz, 4H), 1.61–1.43 (m, 4H), 1.37–1.34 (m, 1H), 1.26–1.19 (m, 2H), 1.11–1.02 (m, 2H), 0.91 (t, J = 7.2 Hz, 3H). 13 13C NMR (101 MHz, CDCl 3 ) δ 154.8, 146.5, 138.3, 134.0, 128.3, 127.2, 126.6, 115.6, 44.3, 39.8, 37.0, 34.4, 33.6, 20.1, 14.5. IR (neat, cm -1 ) 3336, 2954, 2850, 2360, 1734, 1458, 1261, 815. HRMS (EI) [M] + Calculated for C 21 H 26 O2 94.1984, Found 294.1873.

[0200] Example 50

[0201]

[0202] In a 25 mL Schlenk tube, 4,4'-difluorobiphenyl (0.2 mmol, 46.4 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After the reaction was completed monitored by TLC, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain white solid 2ax (27.2 mg, 75%). M.p. 136.5─137.8 °C; 1 1H NMR (101 MHz, CDCl 3 ) δ 7.48 (dd, 2H), 7.42 (d, J = 8.3 Hz, 2H), 7.10 (t, J = 8.6 Hz, 2H), 6.90 (d, J = 8.3 Hz, 2H), 4.87 (brs, 1H). 1313C NMR (101 MHz, CDCl 3 ) δ 163.3, 160.9, 155.0, 136.9 (d, J = 3.2 Hz), 133.1, 128.4–128.1 (m), 115.7 (d, J = 4.0 Hz), 115.5, 19 19F NMR (376 MHz, CDCl 3 ) δ -116.6 (s). IR (neat, cm -1 ) 3408, 2360, 1599, 1246, 1130, 1014, 808, 669. HRMS (EI) [M] + Calcd for C 12 H 9 FO 188.0632, Found 188.0639.

[0203] Example 51

[0204]

[0205] In a 25 mL Schlenk tube, 4-chloro-4'-fluorobiphenyl (0.2 mmol, 41.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to obtain white powder 2ay (19.5 mg, 48%). M.p. 124.3─125.1 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 7.47–7.42 (m, 4H), 7.38 (d, J = 8.5 Hz, 2H), 6.91 (d, J = 8.6 Hz, 2H), 4.85 (brs, 1H). 13 13C NMR (101 MHz, CDCl 3 ) δ 155.3, 139.2, 132.8, 132.7, 128.9, 128.3, 128.0, 115.8. IR (neat, cm -1 ) 3356, 3294, 2922, 2360, 1610, 1475, 1396, 1265, 1105, 822, 669. HRMS (EI) [M] + Calcd for C12 H 9 ClO₂ 204.0336, Found 204.0342.

[0206] Example 52

[0207]

[0208] In a 25 mL Schlenk tube, 4-bromo-4'-fluorobiphenyl (0.2 mmol, 50 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 5 / 1) to obtain a white solid 2az (25.1 mg, 52%). M.p. 155.3─156.7 °C; 1 ¹H NMR (400 MHz, DMSO-d 6 ) δ 9.64 (s, 1H), 7.57 (d, J = 8.6 Hz, 2H), 7.52 (d, J = 8.6 Hz, 2H), 7.48 (d, J = 8.5 Hz, 2H), 6.85 (d, J = 8.5 Hz, 2H). 13 ¹³C NMR (101 MHz, DMSO-d 6 ) δ 157.8, 139.9, 132.1, 130.04, 128.5, 128.2, 120.1, 116.2. IR (neat, cm -1 ) 3402, 3388, 2360, 1606, 1479, 1263, 1083, 1001, 729, 692. HRMS (EI) [M] + Calcd for C 12 H 9 BrO 247.9831, Found 247.9836.

[0209] Example 53

[0210]

[0211] In a 25 mL Schlenk tube, 4-iodo-4'-fluorobiphenyl (0.2 mmol, 59.6 mg), UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, extraction was performed with diethyl ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 10 / 1) to obtain a bright yellow solid 2ba (18.3 mg, 31%). M.p. 183.6─184.4 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 7.73 (d, J = 8.3 Hz, 2H), 7.44 (d, J = 8.5 Hz, 2H), 7.29 (d, 2H), 6.90 (d, J = 8.5 Hz, 2H), 4.82 (brs, 1H). 13 13C NMR (101 MHz, CDCl 3 ) δ 155.4, 140.3, 137.8, 132.8, 128.6, 128.2, 115.8, 92.2. IR (neat, cm -1 ) 3271, 2853, 2630, 1737, 1614, 1458, 1377, 1265, 1001, 810. HRMS (EI) [M] + Calcd for C 12 H 9 IO 295.9693, Found 295.9699.

[0212] Example 54

[0213]

[0214] In a 25 mL Schlenk tube, 4'-fluoro-[1,1'-biphenyl]-4-yl trifluoromethanesulfonate (0.2 mmol, 64 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, extraction was performed with diethyl ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 10 / 1) to obtain a white solid 2bb (37.5 mg, 59%). M.p. 96.3─97.9 °C; 1 1H NMR (101 MHz, CDCl 3) δ 7.58 (d, J = 8.8 Hz, 2H), 7.44 (d, J = 8.6 Hz, 2H), 7.31 (d, J = 8.8 Hz, 2H), 6.92 (d, J = 8.6 Hz, 2H), 5.04 (s, 1H). 13 C NMR (101 MHz, CDCl 3 ) δ 155.7, 148.5, 141.2, 132.1, 128.5, 128.3, 121.6, 115.9. IR (neat, cm -1 ) 3408, 2924, 2360, 1739, 1610, 1492, 1421, 1230, 1109, 878, 632. HRMS (EI) [M] + Calcd for C 13 H 9 F 3 O 4 S 318.0168, Found 318.0177.

[0215] Example 55

[0216]

[0217] In a 25 mL Schlenk tube, 4'-fluoro-[1,1'-biphenyl]-4-yl methanesulfonate (0.2 mmol, 53.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After monitoring the reaction by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 3 / 1) to obtain a white solid 2bc (32.7 mg, 62%). M.p. 175.8─177.3 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 9.64 (s, 1H), 7.66 (d, J = 8.7 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 7.37 (d, J = 8.7 Hz, 2H), 6.85 (d, J = 8.5 Hz, 2H), 3.39 (s, 3H). 13 13C NMR (101 MHz, DMSO-d 6) δ 157.9, 148.2, 139.8, 130.1, 128.4, 127.9, 123.1, 116.3, 37.8. IR (neat, cm -1 ) 3233, 2920, 2850, 2360, 1608, 1496, 1371, 1153, 875, 794. HRMS (ESI) [M+Na] + Calculated for C 13 H 12 O 4 Na S 287.0349, Found 287.0351.

[0218] Example 56

[0219]

[0220] In a 25 mL Schlenk tube, 3-fluoro-4-chloroacetophenone (0.2 mmol, 34.0 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to obtain a white solid 2bd (23 mg, 74%). M.p. 90.9─92.2 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.62 (s, 1H), 7.45 (d, J = 8.3 Hz, 1H), 7.39 (d, J = 8.3 Hz, 1H), 6.55 (s, 1H), 2.57 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 197.6, 151.9, 137.1, 129.5, 125.6, 121.3, 116.1, 26.7. IR (neat, cm -1 ) 3203, 2878, 2452, 1956, 1699, 1298, 944, 837. HRMS (ESI) [M+H] + Calculated for C 8 H 8 O 2Cl 171.0207, Found 171.0210.

[0221] Example 57

[0222]

[0223] In a 25 mL Schlenk tube, 3-fluoro-4-bromoacetophenone (0.2 mmol, 43.3 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC was completed, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 20 / 1) to obtain a white solid 2be (32 mg, 78%). M.p. 89.6─90.3 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.98 (s, 1H), 7.81 (d, J = 8.5 Hz, 1H), 7.08 (d, J = 8.5 Hz, 1H), 6.45 (s, 1H), 2.56 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 196.2, 155.8, 130.9, 130.0, 129.3, 120.5, 116.2, 26.3. IR (neat, cm -1 ) 3211, 2920, 2850, 2492, 2331, 2142, 1878, 1561, 878. HRMS (ESI) [M+H] + Calculated for C 8 H 8 O 2 Cl 171.0207, Found 171.0208.

[0224] Example 58

[0225]

[0226] In a 25 mL Schlenk tube, 3-chloro-4-fluoroacetophenone (0.2 mmol, 34.0 mg), UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, it was extracted with diethyl ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 5 / 1) to give a white solid 2bf (26.8 mg, 79%). M.p. 89.6─90.3 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.98 (s, 1H), 7.81 (d, J = 8.5 Hz, 1H), 7.08 (d, J = 8.5 Hz, 1H), 6.45 (s, 1H), 2.56 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 196.2, 155.8, 130.9, 130.0, 129.3, 120.5, 116.2, 26.3. IR (neat, cm -1 ) 3211, 2920, 2850, 2492, 2331, 2142, 1878, 1561, 878. HRMS (ESI) [M+H] + Calculated for C 8 H 8 O 2 Cl 171.0207, Found 171.0208.

[0227] Example 59

[0228]

[0229] In a 25 mL Schlenk tube, 3-bromo-4-fluoroacetophenone (0.2 mmol, 43.3 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL). Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC was completed, it was extracted with diethyl ether or ethyl acetate, concentrated, and then by column chromatography (V PE / V EA = 5 / 1) to give a white solid 2bg (34 mg, 83%). M.p. 93.1─94.3 °C; 1 H NMR (400 MHz, CDCl3 ) δ 8.12 (s, 1H), 7.84 (d, J = 8.5 Hz, 1H), 7.07 (d, J = 8.5 Hz, 1H), 6.54 (s, 1H), 2.55 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 196.1, 156.7, 133.2, 131.3, 130.0, 115.9, 110.6, 26.3. IR (neat, cm -1 ) 3122, 2358, 1651, 1560, 1357, 1265, 1041, 821, 717. HRMS (ESI) [M + H] + Calculated for C 8 H 10 O 2 Br 214.9702, Found 214.9705.

[0230] Example 60

[0231]

[0232] In a 25 mL Schlenk tube, 4'-chloro-2'-fluoroacetophenone (0.2 mmol, 34.0 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC and completed, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 2 / 1) to obtain a white solid 2bh (16 mg, 50%). M.p. 87.6─89.3 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 12.38 (s, 1H), 7.64 (d, J = 8.6 Hz, 1H), 6.98 (s, 1H), 6.87 (d, J = 8.6 Hz, 1H), 2.60 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 203.8, 163.0, 142.2, 131.7, 119.6, 118.5, 118.3, 26.7. IR (neat, cm -1)3271,3002,28932418,1750,1489,1272,1060,979,696.HRMS(ESI)[M+H] + Calculated for C 8 H 8 O 2 Cl 171.0129, Found 171.0210.

[0233] Example 61

[0234]

[0235] In a 25 mL Schlenk tube, 4-bromo-2-fluoroacetophenone (0.2 mmol, 43.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and 2N H 2 SO 4 (2 mL) were added. The mixture was irradiated and stirred under an air atmosphere with a blue LED (460 nm, 6 W) for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 20 / 1) to obtain a white solid 2bi (26 mg, 63%). M.p. 40.1─40.8 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 12.31 (s, 1H), 7.52 (d, J = 8.5 Hz, 1H), 7.09 (s, 1H), 6.98 (d, J = 8.5 Hz, 1H), 2.57 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 204.0, 162.7, 131.6, 130.7, 122.5, 121.5, 118.5, 26.7. IR (neat, cm -1 ) 3381, 3072, 2953 2358, 1700, 1589, 1292, 1190, 999, 796. HRMS(ESI)[M+H] + Calculated for C 8 H 10 O 2 Br 214.9702, Found 214.9702.

[0236] Example 62

[0237]

[0238] In a 25 mL Schlenk tube, 4-bromo-2-fluorobiphenyl (0.2 mmol, 50.2 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC to completion, extraction was carried out with diethyl ether or ethyl acetate, followed by concentration, and then 2bj (37 mg, 75%) as a bright yellow oil was obtained by column chromatography (V PE / V EA = 5 / 1). 1 1H NMR (400 MHz, CDCl 3 ) δ 7.53–7.47 (m, 2H), 7.46–7.38 (m, 3H), 7.17 (s, 1H), 7.15–7.08 (m, 2H), 5.36 (s, 1H). 13 13C NMR (101 MHz, CDCl 3 ) δ 153.2, 136.1, 131.3, 129.5, 128.9, 128.3, 127.3, 124.0, 122.1, 119.2. IR (neat, cm -1 ) 3431, 3381, 2922, 2341, 1604, 1475, 1008, 877, 763.

[0239] Example 63

[0240]

[0241] In a 25 mL Schlenk tube, 4,4'-difluorodiphenyl sulfone (0.2 mmol, 50.8 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. Under irradiation and stirring in an air atmosphere with a blue LED (460 nm, 6 W) for 48 h, after monitoring the reaction by TLC to completion, extraction was carried out with diethyl ether or ethyl acetate, followed by concentration, and then 2bk (32 mg, 64%) as a white solid was obtained by column chromatography (V PE / V EA = 10 / 1). M.p. 134.6─136.7 °C; 1 1H NMR (400 MHz, CDCl 3) δ 7.91 (dd, J = 8.9, 5.0 Hz, 2H), 7.78 (d, J = 8.8 Hz, 2H), 7.16 (t, J = 8.6 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 6.52 (s, 1H). 13 C NMR (101 MHz, CDCl 3 ) δ 166.58, 164.04, 160.49, 138.14 (d, J = 3.2 Hz), 132.54, 130.07 (d, J = 9.0 Hz), 116.70, 116.37 (d, J = 19.4 Hz). 19 F NMR (376 MHz, CDCl 3 ) δ -104.5 (s). IR (neat, cm -1 ) 3369, 2926, 2360, 1286, 1071, 833, 686. HRMS (ESI) [M + H] + Calculated for C 12 H 10 O 3 FS253.0329, Found 253.0332.

[0242] Example 64

[0243]

[0244] In a 25 mL Schlenk tube, 4,4'-difluorobenzophenone (0.2 mmol, 43.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to obtain a white solid 2bl (22.8 mg, 55%). M.p. 159.6─161.3 °C; 1 H NMR (400 MHz, DMSO-d 6 ) δ 10.46 (s, 1H), 7.75 (dd, J = 8.5, 5.7 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.36 (t, J = 8.8 Hz, 2H), 6.90 (d, J = 8.5 Hz, 2H). 13 C NMR (101 MHz, DMSO-d 6) δ 193.5, 165.9, 163.4, 162.3, 135.0 (d, J = 2.9 Hz), 132.9, 132.5 (d, J = 9.2 Hz), 128.3, 116.0, 115.7 (d, J = 12.0 Hz). 19 F NMR (376 MHz, DMSO-d 6 ) δ -107.8 (s). IR (neat, cm -1 ) 3277, 2924, 2341, 1637, 1600, 1508, 1282, 1153, 929, 844. HRMS (ESI) [M + H] + Calculated for C 13 H 10 O 2 F 217.0659, Found 217.0661.

[0245] Example 65

[0246]

[0247] In a 25 mL Schlenk tube, 2,4'-difluorobenzophenone (0.2 mmol, 43.6 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After monitoring the reaction by TLC until completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 10 / 1) to obtain a pale yellow solid 2bm (21 mg, 53%). M.p. 85.6 - 86.3 °C; 1 1H NMR (400 MHz, CDCl 3 ) δ 7.81–7.76 (m, 2H), 7.50 (dd, J = 9.7, 4.6 Hz, 2H), 7.24 (t, J = 5.5 Hz, 1H), 7.15 (t, J = 9.2 Hz, 1H), 6.90 (d, J = 8.7 Hz, 2H), 6.63 (s, 1H). 13 13C NMR (101 MHz, CDCl 3) δ 192.7, 161.0 (d, J = 2.6 Hz), 158.6, 133.0–132.6 (m), 130.5 (d, J = 3.0 Hz), 130.0, 127.2 (d, J = 15.3 Hz), 124.3 (d, J = 3.6 Hz), 116.4, 116.2, 115.5. 19 F NMR (376 MHz, CDCl 3 ) δ -111.8 (s). IR (neat, cm -1 ) 3284, 2922, 2358, 1645, 1577, 1448, 1312, 1219, 1145, 848, 756. HRMS (ESI) [M+Na] + Calculated for C 13 H 9 O 2 FNa 239.0479, Found 239.0479.

[0248] Example 66

[0249]

[0250] In a 25 mL Schlenk tube, 1-(4-fluorophenyl)-(3R)-[3-(4-fluorophenyl)-(3S)-hydroxypropyl]-(4S)-(4-hydroxyphenyl)-2-propiolactam (0.2 mmol, 81.8 mg), UO 2 (OAc) 2 ·2H 2 O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL) were added. The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 3 / 1) to obtain a yellow solid 2bn (37.4 mg, 46%). M.p. 79.6─81.2 °C; 1 1H NMR (400 MHz, DMSO-d 6)δ9.50(s,1H),9.26(brs,1H),7.30(dd,J=8.6,5.7Hz,2H),7.18(d,J=8.5Hz,2H),7.11(t,J=8.9Hz,2H),7.02(d,J=8.8Hz,2H),6.74(d,J=8.5Hz,2H),6.65(d,J=8.8Hz,2H),5.28(d,J=4.5Hz,1H),4.69(d,J=2.0Hz,1H),4.48(t,J=4.9Hz,1H),3.04–2.94(m,1H),1.82–1.65(m,4H). 13 C NMR(101MHz,DMSO-d 6 )δ167.1,162.,160.3,157.7,153.9,142.6,130.1,128.9,129.0–127.0(m),118.6,115.9(dd,J=17.8,8.8Hz),115.1(d,J=21.1Hz),79.6,71.5(d,J=10.7Hz),59.7(d,J=29.5Hz),36.9,25.1. 19 FNMR(376MHz,DMSO-d 6 )δ-116.4(s).IR(neat,cm -1 )3307,2920,2850,2360,1705,1521,1456,1377,1221,881,734.HRMS(ESI)[M+Na] + Calculated for C 24 H 22 O 4 NFNa 430.1425,Found 430.1432.

[0251] Example 67

[0252]

[0253] In a 25 mL Schlenk tube, (4S)-3-[5-(4-fluorophenyl)-1,5-dioxopentyl]-4-phenyl-2-oxazolidinone (0.2 mmol, 71 mg) and UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). The mixture was irradiated and stirred for 48 h under a blue LED (460 nm, 6 W) in air. After completion of the reaction monitored by TLC, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 2 / 1) to give white powder 2bo (45 mg, 64%). M.p. 145.5─147.2 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.36 (s, 1H), 7.81 (d, J = 8.6 Hz, 2H), 7.38 (t, J = 7.2 Hz, 2H), 7.30 (dd, J = 13.2, 7.0 Hz, 3H), 6.83 (d, J = 8.7 Hz, 2H), 5.45 (dd, J = 8.6, 3.5 Hz, 1H), 4.72 (t, J = 8.7 Hz, 1H), 4.15 (dd, J = 8.7, 3.5 Hz, 1H), 3.00–2.85 (m, 4H), 1.87–1.75 (m, 2H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 198.1, 172.4, 162.3, 154.2, 140.47, 130.8, 129.3, 128.4, 126.2, 115.6, 70.7, 57.4, 36.8, 34.7, 19.1. IR (neat, cm -1 ) 3363, 2920, 2358, 1707, 1656, 1598, 1284, 1102, 985, 769, 605. HRMS (ESI) [M+H] + Calculated for C 20 H 20 O 5 N 354.1336, Found 354.1333.

[0254] Example 68

[0255]

[0256] In a 25 mL Schlenk tube, 2-[2-(4-fluorophenyl)-2-oxo-1-phenylethyl]-4-methyl-3-oxo-N-phenylpentanamide (0.2 mmol, 46.4 mg), UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and HFIP (2 mL). The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then purified by column chromatography (V PE / V EA = 3 / 1) to obtain a white solid 2bp (58 mg, 70%). M.p. 166.9─168.2 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.40 (s, 1H), 10.16 (s, 1H), 7.92 (d, J = 8.6 Hz, 2H), 7.34 (d, J = 7.4 Hz, 2H), 7.29 (d, J = 7.7 Hz, 2H), 7.26–7.18 (m, 4H), 7.11 (t, J = 7.3 Hz, 1H), 7.00 (t, J = 7.3 Hz, 1H), 6.80 (d, J = 6.8 Hz, 2H), 5.35 (d, J = 11.0 Hz, 1H), 4.84 (d, J = 11.0 Hz, 1H), 2.98–2.79 (m, 1H), 1.15 (d, J = 7.0 Hz, 3H), 0.93 (d, J = 6.7 Hz, 3H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 208.4, 196.3, 165.6, 162.6, 138.6, 136.5, 131.8, 129.1, 127.8, 127.5, 124.4, 120.1, 115.7, 63.4, 51.9, 19.3, 18.4. IR (neat, cm -1 ) 3278, 2960, 2341, 1714, 1657, 1446, 1215, 989, 833, 692. HRMS (ESI) [M+H] + Calculated for C 26 H 26 O 4 N 416.1856, Found 416.1818.

[0257] Example 69

[0258]

[0259] In a 25 mL Schlenk tube, N-(3-chloro-4-fluorophenyl)-7-fluoro-6-nitro-4-quinazolinamine (0.2 mmol, 67.2 mg) and UO 2 (OAc) 2 ·2H 2O (8 mol% / 0.016 mmol, 6.8 mg), and AcOH (2 mL). The mixture was irradiated and stirred under a blue LED (460 nm, 6 W) in an air atmosphere for 48 h. After the reaction was monitored by TLC to completion, it was extracted with diethyl ether or ethyl acetate, concentrated, and then yellow solid 2bq (33.5 mg, 73%) was obtained by column chromatography (50.7 mg, 76%). M.p. 257.9─259.8 °C; 1 1H NMR (400 MHz, DMSO-d 6 ) δ 10.36 (s, 1H), 10.21 (brs, 1H), 9.55 (d, J = 8.0 Hz, 1H), 8.64 (s, 1H), 7.83 (d, J = 2.5 Hz, 1H), 7.78 (d, J = 12.6 Hz, 1H), 7.52 (dd, J = 8.8, 2.5 Hz, 1H), 7.01 (d, J = 8.8 Hz, 1H). 13 13C NMR (101 MHz, DMSO-d 6 ) δ 159.1, 158.6, 155.5, 154.5, 150.8, 135.7, 130.7, 125.1, 124.9, 123.6, 119.4, 116.7, 115.4, 111.7. 19 19F NMR (376 MHz, DMSO-d 6 ) δ -114.3 (s). IR (neat, cm -1 ) 3309, 2924, 2341, 1734, 1538, 1436, 1361, 1155, 1022, 769, 650. HRMS (ESI) [M + H] + Calculated for C 14 H 9 O 3 N 4 ClF 335.00342, Found 335.00348.

[0260] The protection scope of the present invention is not limited to the above embodiments. Without departing from the spirit and scope of the inventive concept, changes and advantages that can be conceived by those skilled in the art are included in the present invention, and the scope of protection is defined by the appended claims.

Claims

1. A synthetic method for the hydroxylation of aryl fluoride compounds to form arylphenol compounds by uranium photocatalysis, characterized in that, in the synthetic method, the aryl fluoride compound shown in formula (1) is used as a reaction raw material, and in a light environment and a solvent, under the action of a catalyst and with acid assistance, the arylphenol compound shown in formula (2) is obtained through a reaction, and the reaction process is as shown in reaction formula (a); wherein, Ar is selected from a benzene ring, a benzene ring with substituents, a naphthalene ring, a benzheterocycle, a biphenyl ring; the substituents include one or several of C1-C5 alkyl, C1-C5 alkoxy, halogen, acyl, cyano, nitro, hydroxyl, free carboxylic acid, free amino, aromatic heterocycle and / or polycycle.

2. The method according to claim 1, characterized in that, the Ar is selected from one or several of phenyl, p-acetylphenyl, p-nitrophenyl, p-methylsulfonylphenyl, p-tert-butylphenyl, p-methoxyphenyl, p-fluorophenyl, p-methoxyphenyl, p-cyanophenyl, p-formate phenyl, m-formate phenyl, m-cyanophenyl, p-methoxyphenyl, o-cyanophenyl, o-acetylphenyl, o-methoxycarbonylphenyl, substituted indolylphenyl, amino acid derivatives.

3. The method according to claim 1, characterized in that, the catalyst is a photocatalyst, selected from any one or several of uranyl acetate, uranyl nitrate, zinc uranyl acetate, uranyl sulfate, uranium carbonate, uranyl chloride; the dosage of the catalyst is 2-8 mol% of the aryl fluoride compound shown in formula (1).

4. The method according to claim 1, characterized in that, the acid is a Lewis acid, selected from any one or several of sulfuric acid, formic acid, acetic acid, hydrochloric acid, methanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, hydrobromic acid, trifluoromethanesulfonic acid, phosphoric acid, ferric trichloride, zinc chloride; the molar dosage of the acid is 4-10 equivalents of the aryl fluoride compound shown in formula (1).

5. The method according to claim 1, characterized in that, the solvent is water or an organic solvent, and the organic solvent is selected from any one or several of acetic acid, acetonitrile, hexafluoroisopropanol; the dosage of the solvent is 2-45 ml; and / or, the concentration of the aryl fluoride compound shown in formula (1) in the solvent is 0.02-0.2 mol / L.

6. The method according to claim 1, characterized in that, the light source used in the light environment is a blue light source with a wavelength of 430-460 nm and a power of 1-100 W; the illumination time is 1-3 days; and / or, the reaction temperature is 0-40 °C; the reaction time is 1-3 days.

7. The method according to claim 5, characterized in that, when the solvent is water, the molar ratio of the aryl fluoride compound to water is 1:5 to 1:

10.

8. An arylphenol compound obtained by the method according to any one of claims 1-7.

9. The arylphenol compound according to claim 8, characterized in that, the arylphenol compound includes the following:

10. The method according to any one of claims 1-7, or the use of the arylphenol compound according to claim 8 in the hydrolysis of aryl fluoride compounds, the hydroxylation of aryl fluoride compounds, the defluorination hydration of aryl fluoride compounds, the synthesis of arylphenol compounds, the preparation of arylphenol drugs, and the transformation of arylphenol drugs.

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