A method for synthesizing an aromatic aldehyde

Abstract

The application discloses a synthesis method of aromatic aldehyde, comprising the following steps: under inert atmosphere, a compound shown in formula I and a compound shown in formula II are reacted in an organic solvent containing a photocatalyst, a nickel catalyst, a ligand, a base and water under blue light irradiation to obtain aromatic aldehyde shown in formula III; formula I, formula II and formula III are structures as follows, ring A is selected from benzene, pyridine, thiophene, furan, pyridazine, indazole, indole, isoquinoline, quinoline, naphthalene, benzothiophene, dibenzofuran or dibenzothiophene; the application generates formyl radicals under the nickel synergistic photo-oxidation and reduction catalytic condition, and the formylation of bromobenzene and its derivatives is realized in a simple and efficient one-pot way, aromatic aldehyde is constructed, and the reaction has the characteristics of cheap and easily available raw materials, mild reaction conditions, controllable synthesis process, high separation yield / yield, green environmental protection, wide substrate applicability and the like.

Description

Technical Field

[0001] This invention belongs to the field of organic compounds and organic synthesis technology, and particularly relates to a method for synthesizing aromatic aldehydes. Background Technology

[0002] Aromatic aldehydes, as an important class of organic compounds, are among the most widely used intermediates in the synthesis of pharmaceuticals, fragrances, fine chemicals, and natural products. They possess significant industrial value and are crucial chemical raw materials. Therefore, the synthesis of aromatic aldehydes has been a hot topic and a highly challenging area of ​​research for organic and medicinal chemists for decades. Despite their extremely wide range of applications, their preparation methods are very limited.

[0003] Traditional methods for preparing aromatic aldehydes, such as the addition of Grignard reagents to N,N-dimethylformamide (DMF) at low temperatures, suffer from regioselectivity at the expense of functional group compatibility. To date, the most common method for synthesizing aromatic aldehydes is palladium-catalyzed reductive carbonylation of aryl iodides and bromides, first reported by Heck in 1974, conducted in syngas (1:1 H₂ / CO) at 150 °C and 100 atm. Although this reaction has been carried out on a tonne-scale, it still faces limitations due to the use of highly toxic carbon monoxide and specialized equipment for handling high-pressure syngas. To develop more environmentally friendly methods, the Stille and Buchman groups reported the efficient selective formylation of haloaromatics using alternative condensed-phase reducing agents and CO substitutes (such as crystalline N-formyl saccharin). Nevertheless, this reductive formylation reaction remains limited to simple aromatics due to the use of high reaction temperatures and stoichiometric reducing agents.

[0004] Therefore, developing easier and milder reaction methods for synthesizing aromatic aldehydes is a current research hotspot and challenge. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the background art above and provide a green and mild method for synthesizing aromatic aldehydes.

[0006] To solve the above-mentioned technical problems, the technical solution proposed by this invention is as follows:

[0007] A method for synthesizing an aromatic aldehyde, comprising the following steps:

[0008] Under an inert atmosphere, the compounds shown in Formula I and Formula II are reacted in an organic solvent containing a photocatalyst, a nickel catalyst, a ligand, a base, and water under blue light irradiation to obtain the aromatic aldehyde shown in Formula III.

[0009] Equations I, II, and III have the following structure:

[0010]

[0011] Wherein ring A is benzene, pyridine, thiophene, furan, pyridazine, indazole, indole, isoquinoline, quinoline, naphthalene, benzothiophene, dibenzofuran, or dibenzothiophene;

[0012] R is selected from F, Cl, CH3, t-Bu, OCH3, OBn, COOMe, CH2OH, C(CH3)2OH, Ph, in Indicates the connection site;

[0013] X is selected from Br, Cl, I, or OTs;

[0014] The number of R's is n = 0, 1, or 2.

[0015] As a further improvement, the photocatalyst comprises one or any combination of [Ir(dF(CF3)ppy)2(dtbbpy)][PF6], Ir(ppy)2dtbbpyPF6, or 4CzIPN; and / or

[0016] The nickel catalyst comprises one or a combination of nickel bromide or nickel diacetylacetonate; and / or

[0017] The ligands include one or any combination of bipyridine, 4,4-di-tert-butylbipyridine, or 4,4-di-methoxybipyridine.

[0018] As a further improvement, the amount of the photocatalyst is 0.8 to 1.2% of the molar amount of the compound shown in Formula II.

[0019] As a further improvement, the amount of the nickel catalyst used is 10 to 15% of the molar amount of the compound shown in Formula II.

[0020] As a further improvement, the amount of the ligand used is 10 to 15% of the molar amount of the compound shown in Formula II.

[0021] As a further improvement, the base is a strong base-weak acid salt, and its amount is 150 to 200% of the molar amount of the compound shown in Formula II.

[0022] As a further improvement, the molar ratio of water to the compound shown in Formula II is (20-30):1.

[0023] As a further improvement, the molar ratio of the compound shown in Formula I to the compound shown in Formula II is (1.8–2.2):1.

[0024] As a further improvement, the organic solvent is dichloroethane.

[0025] As a further improvement, the reaction temperature is 20–35°C and the reaction time is 20–30 h.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] This invention utilizes nickel-co-catalyzed photoredox catalysis to generate formyl radicals, achieving a simple and efficient one-pot formylation of bromobenzene and its derivatives to construct aromatic aldehydes. The reaction features readily available and inexpensive raw materials, mild reaction conditions, controllable synthesis process, high separation yield / proportion, environmental friendliness, and broad substrate applicability. This method can be further used for the derivatization of potential drug molecules, such as the later-stage derivatization of vitamin E, fructose, and cholesterol derivatives. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is the reaction mechanism of the present invention. Detailed Implementation

[0030] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.

[0031] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0032] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0033] In some specific embodiments, the method for synthesizing aromatic aldehydes of the present invention includes the following steps:

[0034] Under an inert atmosphere, the compounds shown in Formula I and Formula II are reacted in an organic solvent containing a photocatalyst, a nickel catalyst, a ligand, a base, and water under blue light irradiation to yield the aromatic aldehyde shown in Formula III. The reaction formula is as follows:

[0035]

[0036] The reaction mechanism of this invention is as follows: Figure 1 This invention utilizes the N radical cation generated by the oxidation of reactant II to generate a carbon-centered radical via the cleavage of the C-C bond. The participation of a nickel catalyst facilitates the breaking of the C-C bond and subsequent formation of the C-C bond. The presence of two methyl groups on the N-position of reactant II promotes the breaking of the carbon-carbon bond at the β-position, generating a carbon radical. When only one methyl group is substituted on N, the reaction yield is significantly reduced.

[0037] In some embodiments, the nickel catalyst may be nickel bromide or nickel diacetylacetonate. The preferred amount of nickel catalyst is 10–15% of the molar amount of the compound represented by Formula II. Within this range, the one-pot reaction proceeds smoothly and the separation yield is highest.

[0038] In some embodiments, the photocatalyst may be [Ir(dF(CF3)ppy)2(dtbbpy)][PF6], Ir(ppy)2dtbbpyPF6, or 4CzIPN. The preferred amount of photocatalyst is 0.8–1.2% of the molar amount of the compound represented by Formula II. Within this range, the one-pot reaction proceeds smoothly, and the separation yield is highest.

[0039] In some embodiments, the ligand may be bipyridine, 4,4-di-tert-butylbipyridine, or 4,4-di-methoxybipyridine. The preferred amount of the ligand is 10–15% of the molar amount of the compound represented by Formula II.

[0040] In some embodiments, the base is a strong base-weak acid salt, such as potassium carbonate, sodium carbonate, potassium bicarbonate, or sodium bicarbonate. The preferred amount of base is 150–200% of the molar amount of the compound represented by Formula II.

[0041] In some embodiments, the preferred molar ratio of water to the compound represented by Formula II is (20–30):1. The addition of water greatly promotes the hydrolysis process to aldehyde groups (e.g., Figure 1 Therefore, this invention does not require the addition of additional acids such as hydrochloric acid to promote hydrolysis. Without water, the separation yield would be significantly reduced. The amount of water added within the above-mentioned range ensures the highest separation yield. Adding too little water will have an insignificant effect, while adding too much water will reduce the solubility of the raw materials.

[0042] In some embodiments, the molar ratio of the compound represented by Formula I to the compound represented by Formula II is preferably (1.8 to 2.2):1.

[0043] In some embodiments, dichloroethane is preferred as the organic solvent. Only dichloroethane produces good reaction results; using other solvents will lead to a decrease in the separation yield.

[0044] In some embodiments, the blue light wavelength is 450-500nm.

[0045] In some embodiments, the reaction is carried out at room temperature (20–35°C) for 20–30 hours.

[0046] In the examples below, the nickel catalyst used was nickel bromide, the ligand was dtbbpy (4,4-di-tert-butylbipyridine), the photocatalyst was [Ir(dF(CF3)ppy)2(dtbbpy)][PF6], the base was potassium carbonate, and the solvent was dichloroethane. Chromatographic column purification used ethyl acetate and petroleum ether (ethyl acetate volume ratio 1%–5%) as eluents.

[0047] Example 1

[0048] To a 15 mL reaction tube equipped with a magnetic stir bar, nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Subsequently, I-1 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then placed under irradiation with a 30 W blue LED at room temperature.

[0049]

[0050] The mixture was stirred for 24 hours. Subsequently, the reaction solution was dried under vacuum and purified by column chromatography to obtain colorless liquid III-1. The separation yield (molar percentage of product / compound II, the same below) was 63%. The liquid was characterized by NMR.

[0051] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ10.03 (s, 1H), 7.89 (d, J = 7.0Hz, 2H), 7.64 (t, J = 7.4Hz, 1H), 7.54 (t, J = 7.5Hz, 2H) ppm.

[0052] By comparing with the original NMR of known compounds, the structure of product III-1 in this embodiment can be obtained as follows:

[0053]

[0054] Example 2

[0055] To a 15 mL reaction tube equipped with a magnetic stir bar, add nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol). The reaction system was then protected with argon gas. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Subsequently, the mixture was subjected to a 250 mL flow rate.

[0056]

[0057] I-2 (0.8 mmol) and H2O (12.0 mmol) were added to the reaction mixture using a 100 μL syringe. II (0.4 mmol) was then added to the reaction mixture using a 100 μL syringe. The reaction mixture was then stirred for 24 hours at room temperature under 30 W blue LED illumination. Subsequently, the reaction solution was evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-2 with a separation yield of 60%. The liquid was characterized by NMR.

[0058] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ9.96 (s, 1H), 7.77 (d, J = 8.1Hz, 2H), 7.33 (d, J = 7.9Hz, 2H), 2.44 (s, 3H) ppm.

[0059] By comparing with the original NMR spectra of known compounds, the structure of product III-2 in this embodiment can be obtained as follows:

[0060]

[0061] Example 3

[0062] Add nickel catalyst (13 mol%) and ligand (13 mol%) to a 15 mL reaction tube equipped with a magnetic stir bar.

[0063]

[0064] A photocatalyst (1 mol%) and a base (0.8 mmol) were used. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-3 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-3 with a separation yield of 80%. The liquid was characterized by NMR.

[0065] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ9.98 (s, 1H), 7.82 (d, J = 8.4Hz, 2H), 7.55 (d, J = 8.3Hz, 2H), 1.36 (s, 9H) ppm.

[0066] By comparing with the original NMR spectra of known compounds, the structure of product III-3 in this embodiment can be obtained as follows:

[0067]

[0068] Example 4

[0069] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Subsequently, I-4 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-4 with a separation yield of 55%. The liquid was characterized by NMR.

[0070]

[0071] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ9.99 (s, 1H), 7.82 (d, J = 8.4Hz, 2H), 7.51 (d, J = 8.4Hz, 2H) ppm.

[0072] By comparing with the original NMR of known compounds, the structure of product III-4 in this example is as follows:

[0073]

[0074] Example 5

[0075] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Subsequently, I-5 (0.8 mmol) and water (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow solid III-5 with a separation yield of 45%. The liquid was characterized by NMR.

[0076]

[0077] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ9.87 (s, 1H), 7.83 (d, J = 8.7Hz, 2H), 7.49–7.29 (m, 5H), 7.07 (d, J = 8.7Hz, 2H), 5.14 (s, 2H) ppm.

[0078] By comparing with the original NMR spectra of known compounds, the structure of product III-5 in this example is as follows:

[0079]

[0080] Example 6

[0081] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Subsequently, I-6 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a white solid III-6 with a separation yield of 70%. The liquid was characterized by NMR.

[0082]

[0083] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ10.04(s,1H),7.93(d,J=8.3Hz,2H),7.73(d,J=8.2Hz,2H),7.66–7.59(m,2H),7.49–7.38(m,3H)ppm.

[0084] By comparing with the original NMR spectra of known compounds, the structure of product III-6 in this example is as follows:

[0085]

[0086] Example 7

[0087] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-7 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-7 with a separation yield of 30%. The liquid was characterized by NMR.

[0088]

[0089] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ9.97 (s, 1H), 8.11–7.82 (m, 2H), 7.29–7.16 (m, 2H) ppm.

[0090] By comparing with the original NMR spectra of known compounds, the structure of product III-7 in this embodiment can be obtained as follows:

[0091]

[0092] Example 8

[0093] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-8 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-8 with a separation yield of 59%. The liquid was characterized by NMR.

[0094]

[0095] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ9.99 (s, 1H), 7.82 (d, J = 8.4Hz, 2H), 7.51 (d, J = 8.4Hz, 2H) ppm.

[0096] By comparing with the original NMR spectra of known compounds, the structure of product III-8 in this embodiment can be obtained as follows:

[0097]

[0098] Example 9

[0099] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-9 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-9 with a separation yield of 37%. The liquid was characterized by NMR.

[0100]

[0101] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ9.99 (s, 1H), 7.82 (d, J = 8.4Hz, 2H), 7.51 (d, J = 8.4Hz, 2H) ppm.

[0102] By comparing with the original NMR spectra of known compounds, the structure of product III-9 in this example is as follows:

[0103]

[0104] Example 10

[0105] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-10 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-10 with a separation yield of 48%. The liquid was characterized by NMR.

[0106]

[0107] The NMR test results are as follows: 1H NMR (CDCl3, 400MHz) δ9.98 (s, 1H), 7.86 (d, J = 8.1Hz, 2H), 7.52 (d, J = 7.9Hz, 2H), 4.79 (s, 2H), 2.41 (s, 1H) ppm.

[0108] By comparing with the original NMR spectra of known compounds, the structure of product III-10 in this embodiment can be obtained as follows:

[0109]

[0110] Example 11

[0111] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-11 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-11 with a separation yield of 53%. The liquid was characterized by NMR.

[0112] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ9.97 (s, 1H), 7.84 (d, J = 8.4Hz, 2H), 7.66 (d, J = 8.3Hz, 2H), 2.33 (s, 1H), 1.61 (s, 6H) ppm.

[0113] 13 C{ 1 H}NMR (100MHz, CDCl3) δ192.1,156.2,134.9,129.8,125.2,72.5,31.7ppm;

[0114] The mass spectrometry results are: HRMS(ESI) m / z: [M+Na] + Calcd for C 10 H 12 NaO2 + 187.0730; Found 187.0722.

[0115]

[0116] The infrared test results are: IR(neat)ν 1688, 1607, 1289, 1215, 1168, 1089, 832, 705 cm⁻¹ -1 ;

[0117] By comparing with the original NMR spectra of known compounds, the structure of product III-11 in this embodiment can be obtained as follows:

[0118]

[0119] Example 12

[0120] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-12 (0.8 mmol) and H2O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid III-12 with a separation yield of 64%. The liquid was characterized by NMR.

[0121]

[0122] The NMR test results are as follows: 1 H NMR (CDCl3, 400MHz) δ10.14 (s, 1H), 8.31 (s, 1H), 8.06–7.84 (m, 4H), 7.60 (ddd, J = 22.7, 8.2, 6.9Hz, 2H) ppm.

[0123] By comparing with the original NMR spectra of known compounds, the structure of product III-12 in this embodiment can be obtained as follows:

[0124]

[0125] Example 13

[0126] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-13 (0.8 mmol) and H2O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid, III-13, which was then separated.

[0127]

[0128] The yield was 25%, and the yellow solid was subjected to NMR, IR, and mass spectrometry tests.

[0129] The NMR test results are as follows: 1 H NMR(CDCl3,400MHz)δ10.08(s,1H),8.24(s,1H),7.95–7.85(m,2H),7.79(d,J= 8.5Hz,1H),7.22(dd,J=8.9,2.5Hz,1H),7.17(d,J=2.5Hz,1H),3.95(s,3H)ppm;

[0130] 13 C{ 1 H}NMR (100MHz, CDCl3) δ192.0,160.3,138.3,134.2,132.4,131.1,128.0,127.7,123.7,119.9,106.1,55.5ppm;

[0131] The mass spectrometry test results are as follows: HRMS(ESI) m / z: [M]Calcd for C 12 H 10 O2 186.0681; Found 186.0687.

[0132] The infrared test results are: IR(neat)ν 1675, 1622, 1478, 1392, 1267, 1172, 860, 803 cm⁻¹ -1 .

[0133] Based on the results of NMR, IR, and mass spectrometry tests, the structure of product III-13 in this embodiment is as follows:

[0134]

[0135] Example 14

[0136] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-14 (0.8 mmol) and H2O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a colorless liquid, III-14, which was then separated.

[0137]

[0138] The yield was 57%, and the yellow solid was subjected to NMR, IR, and mass spectrometry tests.

[0139] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.11(s,1H),8.56(s,1H),8.23–8.14(m,1H),7.97–7.87(m,2H),7.88–7.81(m,1H),7.56–7.45(m,2H)ppm;

[0140] 13 C{ 1 H}NMR (100MHz, CDCl3) δ191.7,146.0,139.7,135.9,134.9,133.2,127.6,126.9,125.1,123.4,123.2,122.9,121.9ppm;

[0141] The mass spectrometry results are: HRMS(ESI) m / z: [M+H] + Calcd for C 13 H9OS + 213.0369; Found 213.0367.

[0142] The infrared test results are: IR(neat)ν 1693, 1587, 1418, 1316, 1180, 1077, 893, 758 cm⁻¹ -1 .

[0143] Based on the results of NMR, IR, and mass spectrometry tests, the structure of product III-14 in this embodiment is as follows:

[0144]

[0145] Example 15

[0146] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-15 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow solid, III-15, with a separation yield of 51%. The yellow solid was analyzed by NMR.

[0147]

[0148] The NMR test results are as follows: 1 H NMR(400MHz, CDCl3)δ10.56(s,1H),8.14(d,J=7.6Hz,1H),8.00–7.87(m,2H),7.66(d, J=8.3Hz,1H),7.51(t,J=7.8Hz,1H),7.44(t,J=7.6Hz,1H),7.39(t,J=7.1Hz,1H)ppm.

[0149] By comparing with the original NMR spectra of known compounds, the structure of product III-15 in this example is as follows:

[0150]

[0151] Example 16

[0152] To a 15 mL reaction tube equipped with a magnetic stir bar, nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added. The reaction system was then protected with argon. Under argon atmosphere, dry solvent (4.0 mL) was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Subsequently, I-16 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. The solution was injected via a 100 μL syringe.

[0153]

[0154] II (0.4 mmol) was added to the reaction mixture. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. Subsequently, the reaction solution was evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow solid III-16 with a separation yield of 28%. The yellow solid was subjected to NMR analysis.

[0155] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.20 (s, 1H), 9.05 (d, J = 4.2Hz, 1H), 8.39–8.29 (m, 2H), 8.28–8.13 (m, 2H), 7.53 (dd, J = 8.3, 4.2Hz, 1H) ppm.

[0156] By comparing with the original NMR spectra of known compounds, the structure of product III-16 in this example is as follows:

[0157]

[0158] Example 17

[0159] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-17 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow solid, III-17, with a separation yield of 25%. The yellow solid was analyzed by NMR.

[0160]

[0161] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.26(s,1H),9.37(s,1H),8.64(s,1H),8.20(d,J=8.5H z,1H),8.00(d,J=8.6Hz,1H),7.89(t,J=8.4Hz,1H),7.67(t,J=8.0Hz,1H)ppm.

[0162] By comparing with the original NMR spectra of known compounds, the structure of product III-17 in this example is as follows:

[0163]

[0164] Example 18

[0165] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-18 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then vacuum evaporated to dryness and purified by column chromatography to obtain a yellow liquid. The yield of III-18 was 38%, and the yellow liquid was analyzed by NMR.

[0166]

[0167] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.14(s,1H),8.68(d,J=7.7Hz,1H),8.30(s,1H),7.87(d,J=7.9Hz,1H),7.54–7.42(m,2H)ppm.

[0168] By comparing with the original NMR of known compounds, the structure of product III-18 in this example is as follows:

[0169]

[0170] Example 19

[0171] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-19 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then vacuum evaporated to dryness and purified by column chromatography to obtain a colorless liquid, III-19, with a separation yield of 51%. The colorless liquid was analyzed by NMR, IR, and mass spectrometry.

[0172]

[0173] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.01(s,1H),7.90(d,J=8.2Hz,2H),7.61(d,J=8.0Hz,2H),7.14(d,J=7.7Hz,1H),6.79 (d,J=7.7Hz,1H),6.70(s,1H),5.13(s,2H),3.38(hept,J=6.9Hz,1H),2.31(s,3H),1.24(d,J=6.9Hz,6H)ppm;

[0174] 13 C{ 1 H}NMR (100MHz, CDCl3) δ191.9,155.4,144.7,136.5,135.9,134.4,130.0,127.2,126.2,121.9,112.7,69.3,26.7,22.9,21.4ppm;

[0175] The mass spectrometry test results are as follows: HRMS(ESI) m / z: [M]Calcd for C 18 H 20 O2 268.1463; Found 268.1484.

[0176] The infrared test results are: IR(neat)ν 3049, 2958, 2066, 1599, 1505, 1191, 799, 473 cm⁻¹ –1 .

[0177] Based on the results of NMR, IR, and mass spectrometry measurements, the structure of product III-19 in this embodiment is as follows:

[0178]

[0179] Example 20

[0180] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-20 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow solid, III-20, with a separation yield of 43%. The yellow solid was analyzed by NMR, IR, and mass spectrometry.

[0181]

[0182] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ9.95 (s, 1H), 7.73 (s, 1H), 7.70 (d, J = 7.7Hz, 1H), 7.50–7.43 (m, 2H), 7.34(d,J=7.7Hz,1H),7.06–6.97(m,3H),6.68(d,J=3.5Hz,1H),4.19(s,2H),2.40(s,3H).

[0183] 19 F{ 1 H}NMR (376MHz, CDCl3) δ-114.87ppm;

[0184] 13 C{ 1 H}NMR(100MHz, CDCl3)δ192.0,162.2(d,J=246.9Hz),144.1,142.0(d,J=10.7Hz),139.2,135.0,131.2 ,130.7,130.6,128.5,127.2(d,J=7.9Hz),126.3,122.78,122.77,115.8(d,J=21.7Hz),33.9,20.0ppm;

[0185] The mass spectrometry results are as follows: HRMS(ESI) m / z: [M+CH3CN+H] + Calcd for C 21 H 19 FNOS + 352.1166; Found 352.1176.

[0186] The infrared test results are: IR(neat)ν 1692, 1606, 1508, 1440, 1233, 1160, 828, 810 cm⁻¹ -1 .

[0187] Based on the results of NMR, IR, and mass spectrometry tests, the structure of product III-20 in this embodiment is as follows:

[0188]

[0189] Example 21

[0190] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-21 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow solid, III-21, with a separation yield of 32%. The yellow solid was analyzed by NMR, IR, and mass spectrometry.

[0191] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.01(s,1H),7.89(d,J=8.0Hz,2H),7.59(d,J=7.9Hz,2H),7.20(d,J=8.6Hz,1H),6.77(d,J=8.5Hz,1H),6.72(s,1H),5.12(s,2 H),2.95–2.85(m,2H),2.56–2.44(m,1H),2.38(dt,J=13.6,3.7Hz,1H),2. 25(q,J=6.7Hz,1H),2.14–1.89(m,4H),1.64–1.43(m,6H),0.90(s,3H)ppm;

[0192] 13 C{ 1 H}NMR (100MHz, CDCl3) δ191.9,156.4,144.3,138.0,132.8,130.0,127.4,126.5,114 .9,112.3,69.2,50.4,48.0,44.0,38.3,35.9,31.6,29.7,26.5,25.9,21.6,13.9ppm;

[0193] The mass spectrometry results are as follows: HRMS(ESI) m / z: [M+CH3CN+H] + Calcd for C 28 H 32 NO3 + 430.2377; Found 430.2368.

[0194]

[0195] The infrared test results are: IR(neat)ν 1731, 1682, 1610, 1494, 1252, 1161, 1057, 813 cm⁻¹ -1 .

[0196] Based on the results of NMR, IR, and mass spectrometry tests, the structure of product III-20 in this embodiment is as follows:

[0197]

[0198] Example 22

[0199] To a 15 mL reaction tube equipped with a magnetic stir bar, nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added. The reaction system was then protected with argon. Under argon atmosphere, dry solvent (4.0 mL) was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Subsequently, I-22 (0.8 mmol) and H2O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. The solution was injected via a 100 μL syringe.

[0200]

[0201] II (0.4 mmol) was added to the reaction mixture. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. Subsequently, the reaction solution was vacuum evaporated to dryness and purified by column chromatography to obtain a colorless liquid III-22 with a separation yield of 50%. The colorless liquid was analyzed by NMR, IR, and mass spectrometry.

[0202] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.04(s,1H),7.91(d,J=8.1Hz,2H),7.66(d,J=8.0Hz,2H),4.79(s,2H),2.59(t,J=6.8Hz,2H),2.20(s,3H),2.15(s,3H), 2.11(s,3H),1.86–1.74(m,2H),1.62–1.48(m,4H),1.45–1.35(m,4H),1 .31–1.23(d,J=13.8Hz,9H),1.16–1.00(m,7H),0.89–0.84(m,12H)ppm;

[0203] 13 C{ 1 H}NMR(101MHz, CDCl3)δ192.0,147.9,145.1,129.9,127.8,127.6,117.7,74.9,73.8,40.0,39.4,37.50,37.48 ,37.4,37.3,32.8,32.7,31.3,28.0,24.8,24.5,23.9,22.7,22.6,21.0,20.7,19.8,19.7,12.9,12.0,11.8ppm;

[0204] The mass spectrometry results are as follows: HRMS(ESI) m / z: [M+CH3CN+H] + Calcd for C 28 H 32 NO3 + 430.2377; Found 430.2368.

[0205] The infrared test results are: IR(neat)ν 1731, 1682, 1610, 1494, 1252, 1161, 1057, 813 cm⁻¹ -1 .

[0206] Based on the results of NMR, IR, and mass spectrometry tests, the structure of product III-22 in this embodiment is as follows:

[0207]

[0208] Example 23

[0209] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Then, I-23 (0.8 mmol) and H2O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow liquid. The yield of III-23 was 31%, and the yellow liquid was analyzed by NMR.

[0210] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.11 (s, 1H), 8.25–8.16 (m, 2H), 7.95 (d, J = 8.3Hz, 2H), 4.97(td,J=10.9,4.4Hz,1H),2.14–2.09(m,1H),1.95(pd,J=7.0,2.8Hz,1H),

[0211]

[0212] 1.81–1.69(m,2H),1.64–1.51(m,2H),1.22–1.07(m,2H),0.94(dd,J=6.8,4.4Hz,7H),0.81(d,J=6.9Hz,3H)ppm.

[0213] Based on the NMR test results, the structure of product III-23 in this embodiment is as follows:

[0214]

[0215] Example 24

[0216] Nickel catalyst (13 mol%), ligand (13 mol%), photocatalyst (1 mol%), and base (0.8 mmol) were added to a 15 mL reaction tube equipped with a magnetic stir bar. The reaction system was then protected with argon. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. I-24 (0.8 mmol) and H2O (12.0 mmol) were then added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred for 24 hours under 30 W blue LED illumination at room temperature. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow liquid. The yield of III-24 was 30%. The yellow liquid was analyzed by NMR, IR, and mass spectrometry.

[0217]

[0218] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.11(s,1H),8.24(d,J=8.3Hz,2H),7.96(d,J=8.3Hz,2H),4.72(d,J=11.7Hz,1H),4.65(d,J=7.9Hz,1H),4.45(d,J=2.6Hz,1H), 4.37(d,J=11.7Hz,1H),4.27(d,J=7.9Hz,1H),3.96(d,J=13.0Hz,1H),3.81 (d,J=13.0Hz,1H),1.56(s,3H),1.46(s,3H),1.37(s,3H),1.35(s,3H)ppm;

[0219] 13 C{ 1 H}NMR(101MHz, CDCl3)δ192.0,147.9,145.1,129.9,127.8,127.6,117.7,74.9,73.8,40.0,39.4,37.50,37.48 ,37.4,37.3,32.8,32.7,31.3,28.0,24.8,24.5,23.9,22.7,22.6,21.0,20.7,19.8,19.7,12.9,12.0,11.8ppm;

[0220] The mass spectrometry results are: HRMS(ESI) m / z: [M+H] + Calcd for C 20 H 24 NaO8+ 415.1363; Found 415.1372.

[0221] The infrared test results are: IR(neat)ν 2989,1704,1375,1251,1104,1068,888,756cm -1 ;

[0222] Based on the results of NMR, IR, and mass spectrometry tests, the structure of product III-24 in this embodiment is as follows:

[0223]

[0224] Example 25

[0225] Add nickel catalyst (13 mol%) and ligand (13 mol%) to a 15 mL reaction tube equipped with a magnetic stir bar.

[0226]

[0227] A photocatalyst (1 mol%) and a base (0.8 mmol) were used. The reaction mixture was then protected with argon gas. Under argon atmosphere, 4.0 mL of dry solvent was added via a 5.0 mL syringe, and the mixture was stirred at room temperature for 15 minutes. Subsequently, I-25 (0.8 mmol) and H₂O (12.0 mmol) were added to the reaction mixture via a 250 μL microsyringe. II (0.4 mmol) was added to the reaction mixture via a 100 μL syringe. The reaction mixture was then stirred at room temperature under 30 W blue LED illumination for 24 hours. The reaction solution was then evaporated to dryness under vacuum and purified by column chromatography to obtain a yellow solid, III-25, with a separation yield of 35%. The yellow solid was analyzed by NMR, IR, and mass spectrometry.

[0228] The NMR test results are as follows: 1 H NMR (400MHz, CDCl3) δ10.10(s,1H),8.20(d,J=8.2Hz,2H),7.94(d,J=8.3Hz,2H),5.43(d,J=4.9Hz,1H),5.03–4.75(m,1H),2.48(d,J=7.7Hz,2 H),2.07–1.77(m,6H),1.63–1.47(m,6H),1.42–1.27(m,4H),1.19–0.96 (m,13H),0.92(d,J=6.5Hz,3H),0.87(d,J=6.6Hz,6H),0.69(s,3H)ppm;

[0229] 13 C{ 1H}NMR(101MHz, CDCl3)δ192.0,147.9,145.1,129.9,127.8,127.6,117.7,74.9,73.8,40.0,39.4,37.50,37.48 ,37.4,37.3,32.8,32.7,31.3,28.0,24.8,24.5,23.9,22.7,22.6,21.0,20.7,19.8,19.7,12.9,12.0,11.8ppm;

[0230] The mass spectrometry results are: HRMS(ESI) m / z: [M+H] + Calcd for C 35 H 50 KO3 + 557.3392; Found 557.3389.

[0231] The infrared test results are: IR(neat)ν 2937, 1704, 1270, 1200, 1104, 850, 758, 685 cm⁻¹ -1 .

[0232] Based on the results of NMR, IR, and mass spectrometry measurements, the structure of product III-25 in this embodiment is as follows:

[0233]

[0234] Comparative Example 1

[0235] The only difference from Example 1 is that H2O was not added in this comparative example. The separation yield of product III-1 was 8%.

[0236] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any way. Therefore, any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention should fall within the protection scope of the present invention.

Claims

1. A method for synthesizing aromatic aldehydes, characterized in that, Includes the following steps: Under an inert atmosphere, the starting compound and the compound shown in Formula II are reacted in an organic solvent containing a photocatalyst, a nickel catalyst, a ligand, an alkali, and water under blue light irradiation to convert the Br group in the starting compound into an aldehyde group, yielding an aromatic aldehyde. The raw material compound is selected from the following structures: ； Formula II has the following structure: ； The photocatalyst comprises one or any combination of [Ir(dF(CF3)ppy)2(dtbbpy)][PF6], Ir(ppy)2dtbbpyPF6, or 4CzIPN; the amount of the photocatalyst is 0.8~1.2% of the molar amount of the compound shown in Formula II; The nickel catalyst comprises one or a combination of nickel bromide or nickel diacetylacetonate; the amount of the nickel catalyst used is 10-15% of the molar amount of the compound represented by Formula II; The ligand comprises one or any combination of bipyridine, 4,4-di-tert-butylbipyridine, or 4,4-di-methoxybipyridine; the amount of the ligand used is 10-15% of the molar amount of the compound represented by Formula II. The base is a strong base-weak acid salt, and its amount is 150-200% of the molar amount of the compound shown in Formula II; The molar ratio of water to the compound shown in Formula II is (20~30):1; The reaction temperature is 20~35℃.

2. The method for synthesizing aromatic aldehydes according to claim 1, characterized in that, The molar ratio of the raw material compound and the compound shown in Formula II is (1.8~2.2):

1.

3. The method for synthesizing aromatic aldehydes according to claim 1, characterized in that, The organic solvent is dichloroethane.

4. The method for synthesizing aromatic aldehydes according to claim 1, characterized in that, The reaction time is 20-30 hours.

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