A method for preparing dicarboxylic acid compounds from olefins

Abstract

The present invention discloses a method for preparing dicarboxylic acid compounds from olefins. The method includes: subjecting a mixed reaction system containing an olefin compound, an inorganic base, oxalate, a photosensitive catalyst and a solvent to a photoirradiation reaction to obtain a dicarboxylic acid compound. The method for preparing dicarboxylic acid compounds from olefins provided by the present invention has the advantages of good substrate compatibility, no need to externally add CO<subgt;2< / subgt>, high yield, short reaction time, safety and stability, easy operation, etc. At the same time, the obtained dicarboxylic acid compounds play an important role in the fields of biology, medicine, materials, etc.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for preparing dicarboxylic acid compounds from olefins. Background Art

[0002] Succinic acid compounds widely exist in natural molecules, drugs, and material molecules. In the prior art, the methods for synthesizing succinic acid compounds using CO2 can be divided into alkali metal reduction of olefins to capture CO2, electrolysis activation of olefins and CO2, and photo-mediated continuous single electron reduction strategies. However, these methods all require an additional CO2 gas atmosphere.

[0003] The method of alkali metal reduction of olefins to capture CO2 uses alkali metals as reducing agents to directly reduce olefins, and then undergoes a nucleophilic addition reaction with CO2 to achieve the synthesis of succinic acid compounds. This reaction uses sodium and potassium as direct reducing agents, and such extremely strong reducing conditions make it almost impossible for the reactants to carry any groups other than alkyl substituents, which greatly limits the substrate generality of the reaction.

[0004] The method of electrolysis activation of olefins and CO2 realizes the dicarboxylation reaction of olefins through an electrochemical method. Both olefins and carbon dioxide can obtain electrons at the cathode, becoming vinyl radical anions and carbon dioxide radical anions, and then undergoing subsequent reactions to obtain succinic acid compounds. A technology for realizing the dicarboxylation reaction of olefins by combining electrochemistry with metal organic by adding a nickel catalyst in an electrolytic cell has been disclosed in the prior art, but the yield is still not high.

[0005] The photo-mediated continuous single electron reduction strategy is that olefins are reduced by a photosensitizing catalyst to form olefin radical anions. Under a CO2 gas atmosphere, this intermediate can undergo a nucleophilic addition reaction with CO2, and then the generated carbon radical is further reduced to a carbanion, which captures CO2 again to achieve the synthesis of dicarboxylic acid products. However, the above methods all require an external CO2 gas, which is difficult to operate and difficult to quantitatively analyze. Therefore, under non-CO2 gas conditions, there are still many difficulties and challenges in realizing the dicarboxylation of olefins. Summary of the Invention

[0006] The main object of the present invention is to provide a method for preparing dicarboxylic acid compounds from olefins to overcome the deficiencies of the prior art.

[0007] To achieve the foregoing invention object, the technical solutions adopted by the present invention include:

[0008] An embodiment of the present invention provides a method for preparing dicarboxylic acid compounds from olefins, which includes:

[0009] A photoreaction is carried out on a mixed reaction system containing an olefin compound, an inorganic base, an oxalate, a photosensitizing catalyst and a solvent to obtain a dicarboxylic acid compound.

[0010] In some more specific embodiments, the olefin compound includes any one of a monoaryl-substituted olefin compound, a 1,1-diarylethylene compound, a 1,3-diene compound, an N-Boc-substituted indole compound, an allene compound, and a benzofuran compound.

[0011] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0012] (1) The method for preparing a dicarboxylic acid compound from an olefin provided by the present invention is efficient and concise. Using an oxalate as a carboxyl source, the synthesis of a dicarboxylic acid compound can be achieved without adding an external CO2 gas, with high atom economy, simple operation, and broad application prospects;

[0013] (2) The method for preparing a dicarboxylic acid compound from an olefin provided by the invention can synthesize dicarboxylic acid compounds that are difficult to synthesize by other methods, with high yield, mild reaction conditions, low toxicity of reaction reagents, and low cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments described in the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0015] Figure 1 It is a schematic diagram of the reaction mechanism for preparing a dicarboxylic acid compound in a typical embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0016] In view of the defects of the prior art, the inventors of this case have proposed the technical solutions of the present invention through long-term research and a large number of practices. The following will clearly and completely describe the technical solutions of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0017] Specifically, as an aspect of the technical solution of the present invention, a method for preparing a dicarboxylic acid compound from an olefin involves:

[0018] A photoreaction is carried out on a mixed reaction system containing an olefin compound, an inorganic base, an oxalate, a photosensitizing catalyst, and a solvent to obtain a dicarboxylic acid compound.

[0019] In some preferred embodiments, the schematic diagram of the reaction mechanism for preparing a dicarboxylic acid compound from an olefin in the present invention is as Figure 1 shown.

[0020] In some preferred embodiments, the olefin compound includes any one of a monoaryl-substituted olefin compound, a 1,1-diarylethylene compound, a 1,3-diene compound, an N-Boc-substituted indole compound, an allene compound, a benzofuran compound, and is not limited thereto.

[0021] Further, the monoaryl-substituted olefin compound has a structure shown in formula (I):

[0022]

[0023] wherein, R 1 is selected from an alkyl group, an aryl group, a halogen, a cyano group, or a methoxy group, and R 2 , R 3 are independently selected from hydrogen, an alkyl group, or an aryl group.

[0024] Further, the 1,1-diarylethylene compound has a structure shown in formula (II):

[0025]

[0026] wherein, R 4 , R 5 are independently selected from hydrogen, an alkyl group, a methoxy group, or a halogen, and R 6 is selected from hydrogen, an alkyl group, or an aryl group.

[0027] Further, the 1,3-diene compound has a structure shown in formula (III):

[0028]

[0029] wherein, R 7 is selected from hydrogen, an alkyl group, an aryl group, or a halogen, R 8 is selected from hydrogen, an alkyl group, or an aryl group, R 9 , R 10 are independently selected from hydrogen or an alkyl group.

[0030] Further, the N-Boc-substituted indole compound has a structure shown in formula (IV):

[0031]

[0032] wherein, R11 Selected from hydrogen, alkyl, aryl, halogen or ester group.

[0033] In some preferred embodiments, the oxalate includes (NEt4)2C2O4 and / or [N(nBu)4]2C2O4, and is not limited thereto.

[0034] In some preferred embodiments, the photosensitizing catalyst includes any one or a combination of two or more of 4CzIPN, 4DPAIPN, Ir[dF(CF3)ppy]2(dtbbpy)PF6, fac-Ir(ppy)3, and is not limited thereto.

[0035] In some preferred embodiments, the inorganic base includes any one or a combination of two or more of CsF, KF, Cs2CO3, K2CO3, and is not limited thereto.

[0036] In some preferred embodiments, the solvent includes any one or a combination of two or more of DMF, DMA, DMSO, and is not limited thereto.

[0037] In some preferred embodiments, the molar ratio of the photosensitizing catalyst to the olefin compound is 1:100 to 15:100.

[0038] Further, the molar ratio of the photosensitizing catalyst to the olefin compound is 2:100.

[0039] In some preferred embodiments, the molar ratio of the oxalate to the olefin compound is 1:1 to 5:1.

[0040] Further, the molar ratio of the oxalate to the olefin compound is 2:1.

[0041] In some preferred embodiments, the molar ratio of the inorganic base to the olefin compound is 5:1 - 8:1.

[0042] In some preferred embodiments, the method specifically includes: mixing an olefin compound, an inorganic base, an oxalate, a photosensitizing catalyst and a solvent to form the mixed reaction system, and then stirring and reacting at room temperature for 8 - 24 h under a protective atmosphere and under visible light irradiation to obtain the dicarboxylic acid compound.

[0043] In some preferred embodiments, the wavelength of the visible light irradiation is 400 - 450 nm.

[0044] Further, the wavelength of the visible light irradiation is 420 nm.

[0045] In the process of the present invention, the reactants are irradiated with visible light at 400-450 nm (such as 420 nm). The light in this wavelength range is blue light, which has relatively low energy and only acts on the photosensitive catalyst. Moreover, the light in this wavelength range is more easily absorbed by the photosensitive catalyst, which can efficiently activate the photosensitive catalyst and improve the reaction efficiency. In addition, blue light will not be absorbed by organic compounds, so it will not cause the decomposition of compounds, ensuring a high yield of the synthesis reaction.

[0046] In some preferred embodiments, the method further includes: after the reaction is completed, an inorganic acid is added to the obtained mixed solution to carry out a quenching reaction, and then separation and purification are carried out.

[0047] Furthermore, the inorganic acid includes any one of dilute hydrochloric acid, dilute sulfuric acid, and acetic acid.

[0048] In some more specific embodiments, the method for preparing a dicarboxylic acid compound from an olefin includes:

[0049] A substrate, oxalate, a photosensitive catalyst, and an inorganic base are added to a reaction vessel in a molar ratio of 1:2:0.02:5-8, then a solvent is added under a N2 atmosphere, and the reaction is stirred at room temperature for 8-24 h. During the reaction process, the reaction solution is irradiated with visible light having a wavelength of 420 nm; then the reaction is quenched with 1N dilute hydrochloric acid, and then the reaction mixture is separated and purified to obtain a dicarboxylic acid compound.

[0050] In some more specific examples, the method for preparing a dicarboxylic acid compound from an olefin includes the following steps:

[0051] (1) Add 0.2 mmol of an olefin compound and 0.004 mmol of a photosensitive catalyst 4DPAIPN (2 mol%) to a dry reaction tube (2 mL) containing a magnetic stirrer.

[0052] (2) Transfer the Schlenk tube into a glove box, and charge 0.4 mmol of [N(nBu)4]2C2O4 (229.2 mg, 0.4 mmol, 2 equivalents) and 1.0 mmol of CsF (151.9 mg, 1.0 mmol, 5 equivalents) into the reaction tube.

[0053] (3) After closing the reaction tube, take it out of the glove box and connect it to a double manifold connected to a N2 cylinder. Loosen the lid and evacuate and refill with N2 on the double manifold at least 3 times.

[0054] (4) Add 1.5 mL of a solvent DMF to the reaction tube filled with N2.

[0055] (5) Place the reaction tube containing the reaction solution 1 - 2 cm away from a 30 W blue LED lamp (with a wavelength of about 420 nm), and stir the reaction at room temperature (about 25 °C) for 8 - 24 hours.

[0056] (6) Quench the reaction with 3 mL of 1 N hydrochloric acid; extract with ethyl acetate, dry with Na2SO4, and concentrate and spin - dry the quenched reactant in a rotary evaporator. The residue is purified by flash column chromatography. The purification conditions are as follows: first, rinse with a mixture of petroleum ether / ethyl acetate = 10 / 1 (v / v), then rinse with a mixture of petroleum ether / ethyl acetate = 5 / 1 (v / v), and finally elute with a mixture of petroleum ether / ethyl acetate = 1 / 2 (v / v) to obtain the pure product.

[0057] The synthesis method provided by the present invention has the advantages of good substrate compatibility, no need to add external CO2, high yield, short reaction time, safety and stability, and easy operation; the prepared dicarboxylic acid compounds play an important role in the fields of biology, medicine, materials, etc.

[0058] The following further elaborates on the technical solution of the present invention in combination with several preferred embodiments. These embodiments are implemented on the premise of the technical solution of the invention, and detailed implementation methods and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0059] The experimental materials used in the following embodiments can be purchased from conventional biochemical reagent companies without special instructions.

[0060] Example 1

[0061] A method for preparing dicarboxylic acid compounds using mono - aryl - substituted olefin compounds or 1,1 - diarylethylene compounds as reaction substrates includes the following steps:

[0062] (1) Add 0.2 mmol of the reaction substrate (the reaction substrate and reaction formula are shown in Table 1) and 0.004 mmol of the photosensitizer catalyst 4DPAIPN (2 mol%) to a dry reaction tube (2 mL) containing a magnetic stir bar.

[0063] (2) Transfer the Schlenk tube into the glove box, and load 0.4 mmol of [N(nBu)4]2C2O4 (229.2 mg, 0.4 mmol, 2 equivalents) and 1.0 mmol of CsF (151.9 mg, 1.0 mmol, 5 equivalents) into the reaction tube.

[0064] (3) After sealing the reaction tube, take it out of the glove box and connect it to a double - manifold connected to an N2 cylinder. Loosen the lid and evacuate and refill with N2 at least 3 times on the double - manifold.

[0065] (4) Add 1.5 mL of the solvent DMF to the reaction tube filled with N2.

[0066] (5) Place the reaction tube containing the reaction solution 1 - 2 cm away from a 30 w blue LED lamp (with a wavelength of about 420 nm), and stir the reaction at room temperature (about 25 °C) for 8 - 24 hours.

[0067] (6) Quench the reaction with 3 mL of 1 N hydrochloric acid; extract with ethyl acetate, dry with Na2SO4, and concentrate and evaporate the quenched reactant in a rotary evaporator. The residue is purified by flash column chromatography. The purification conditions are as follows: first, rinse with a mixed solution of petroleum ether / ethyl acetate = 10 / 1 (v / v), then rinse with a mixed solution of petroleum ether / ethyl acetate = 5 / 1 (v / v), and finally elute with a mixed solution of petroleum ether / ethyl acetate = 1 / 2 (v / v) to obtain the pure product.

[0068] Table 1 Substrates of mono - aryl - substituted olefin compounds or 1,1 - diarylethylene compounds, their corresponding products, and yields

[0069]

[0070] Performance characterization:

[0071] Among them, product 2a: 2 - phenylsuccinic acid

[0072]

[0073] 24.0 mg, white solid, yield: 62%.

[0074] 1 H NMR (400 MHz, CD3OD) δ 7.33 - 7.23 (m, 5H), 4.01 (dd, J = 10.0, 5.2 Hz, 1H), 3.10 (dd, J = 17.2, 10.0 Hz, 1H), 2.62 (dd, J = 17.2, 5.2 Hz, 1H).

[0075] 13 C NMR (100 MHz, CD3OD) δ 176.7, 175.2, 139.9, 129.8, 128.9, 128.5, 48.7, 38.8.

[0076] ESIHRMS: m / z Calcd. For C 10 H 10 O4: (M + Na) + 217.0471. Found: 217.0468.

[0077] Product 2b: 2-(4-methoxyphenyl)succinic acid, 2-(4-methoxyphenyl)succinic acid

[0078]

[0079] 11.5 mg, white solid, yield: 26%.

[0080] 1 H NMR (400 MHz, CD3OD) δ 7.23 - 7.20 (m, 2H), 6.89 - 6.84 (m, 2H), 3.94 (dd, J = 10.0, 5.2 Hz, 1H), 3.75 (s, 3H), 3.06 (dd, J = 17.2, 10.0 Hz, 1H), 2.58 (dd, J = 17.2, 5.2 Hz, 1H).

[0081] 13 C NMR (100 MHz, CD3OD) δ 176.9, 175.2, 160.5, 131.7, 129.9, 115.1, 55.7, 47.8, 38.8.

[0082] ESIHRMS: m / z Calcd.For C 11 H 12 O5: (M+Na) + 247.0577.Found: 247.0572.

[0083] Product 2c: 2-([1,1′-biphenyl]-4-yl)succinic acid, 2-([1,1′-biphenyl]-4-yl)succinic acid

[0084]

[0085] 33.5 mg, white solid, yield: 62%.

[0086] 1 H NMR (400 MHz, CD3OD) δ 7.62 - 7.55 (m, 4H), 7.45 - 7.37 (m, 4H), 7.32 (t, J = 7.6 Hz, 1H), 4.07 (dd, J = 10.0, 5.2 Hz, 1H), 3.14 (dd, J = 17.2, 10.0 Hz, 1H), 2.67 (dd, J = 17.2, 5.2 Hz, 1H).

[0087] 1313C NMR (100 MHz, CD3OD) δ 176.5, 175.2, 141.9, 141.7, 138.9, 129.9, 129.4, 128.4, 128.3, 127.9, 48.3, 38.7.

[0088] ESIHRMS: m / z Calcd. For C 16 H 14 O4: (M + Na) + 293.0784. Found:.293.0779.

[0089] Product 2d: 2-Methyl-2-phenylsuccinic acid, 2-methyl-2-phenylsuccinic acid

[0090]

[0091] 21.7 mg, white solid, yield: 52%.

[0092] 1 1H NMR (400 MHz, CD3OD) δ 7.46 - 7.36 (m, 2H), 7.36 - 7.27 (m, 2H), 7.27 - 7.19 (m, 1H), 3.21 (d, J = 16.8 Hz, 1H), 2.81 (d, J = 16.8 Hz, 1H), 1.68 (s, 3H).

[0093] 13 13C NMR (100 MHz, CD3OD) δ 178.8, 174.7, 144.7, 129.5, 128.0, 126.8, 49.2, 44.3, 24.0.

[0094] ESIHRMS: m / z Calcd. For C 11 H 12 O4: (M + Na) + 231.0628. Found:.231.0625.

[0095] Product 2e: 2-Cyclopropyl-2-phenylsuccinic acid, 2-cyclopropyl-2-phenylsuccinic acid

[0096]

[0097] 27.9 mg, white solid, yield: 60%.

[0098] 11H NMR (400 MHz, CD3OD) δ 7.34 - 7.26 (m, 4H), 7.23 (dt, J = 6.8, 3.2 Hz, 1H), 3.11 (s, 2H), 1.72 (ddd, J = 14.4, 8.4, 6.0 Hz, 1H), 0.50 (dt, J = 13.2, 6.8 Hz, 1H), 0.43 - 0.30 (m, 1H), 0.05 (p, J = 5.2 Hz, 2H).

[0099] 13 13C NMR (100 MHz, CD3OD) δ 178.4, 174.9, 140.7, 128.9, 128.7, 128.1, 53.6, 42.9, 18.3, 3.7, 1.1.

[0100] ESIHRMS: m / z Calcd. For C 13 H 16 O4: (M + Na) + 259.0941. Found: 259.0931.

[0101] Product 2f. 2 - cyclohexyl - 2 - phenylsuccinic acid

[0102]

[0103] 21.0 mg, white solid, yield: 38%.

[0104] 1 1H NMR (400 MHz, CD3OD) δ 7.38 (d, J = 8.0 Hz, 2H), 7.31 - 7.24 (m, 2H), 7.23 - 7.17 (m, 1H), 3.21 (d, J = 16.8 Hz, 1H), 3.06 (d, J = 16.8 Hz, 1H), 2.13 (t, J = 11.6 Hz, 1H), 1.68 (dt, J = 38.8, 13.2 Hz, 5H), 1.23 (dt, J = 26.0, 10.8 Hz, 2H), 1.08 - 0.77 (m, 3H).

[0105] 13 13C NMR (100 MHz, CD3OD) δ 177.9, 175.6, 142.0, 128.8, 128.7, 127.5, 57.3, 47.1, 40.1, 30.0, 29.9, 28.2, 28.1, 27.6.

[0106] ESIHRMS: m / z Calcd. For C 16 H20 O4: (M + Na) + 299.1254. Found: 299.1244.

[0107] Product 2g: 2,2-diphenylsuccinic acid

[0108]

[0109] 41.9 mg, white solid, yield: 78%.

[0110] 1 H NMR (400 MHz, CD3OD) δ 7.40 - 7.15 (m, 10H), 3.60 - 3.41 (m, 2H).

[0111] 13 C NMR (100 MHz, CD3OD) δ 176.8, 174.4, 144.5, 129.9, 128.8, 127.8, 58.6, 44.8.

[0112] ESIHRMS: m / z Calcd. For C 16 H 14 O4: (M + Na) + 293.0784. Found: 293.0776.

[0113] Product 2h: 2-phenyl-2-(o-tolyl)succinic acid (2h)

[0114]

[0115] 34.8 mg, white solid, yield: 61%.

[0116] 1 H NMR (400 MHz, CD3OD) δ 7.41 - 7.07 (m, 9H), 3.61 (d, J = 15.6 Hz, 1H), 3.40 (d, J = 15.6 Hz, 1H), 1.90 (s, 3H).

[0117] 13 C NMR (100 MHz, CD3OD) δ 176.8, 174.9, 143.8, 142.0, 138.8, 133.5, 130.0, 129.6, 128.8, 128.3, 127.7, 126.4, 59.2, 45.1, 22.0.

[0118] ESIHRMS: m / z Calcd. For C 17 H 16 O4: (M+Na) + 307.0941. Found: 307.0939.

[0119] Product 2i: 2-Phenyl-2-(3,4-difluorophenyl)succinic acid (2i), 2-(3,4-difluorophenyl)-2-phenylsuccinic acid

[0120]

[0121] 40.7 mg, white solid, yield: 66%.

[0122] 1 H NMR (400 MHz, CD3OD) δ 7.36 - 7.23 (m, 6H), 7.15 - 7.02 (m, 2H), 3.60 (d, J = 16.8 Hz, 1H), 3.37 (d, J = 16.8 Hz, 1H).

[0123] 13 C NMR (100 MHz, CD3OD) δ 176.1, 174.2, 150.5 (dd, J FC = 243.3, 12.5 Hz), 150.2 (dd, J FC = 245.4, 12.7 Hz), 143.9, 142.0 (t, J FC = 4.6 Hz), 129.2 (8), 129.2 (5), 128.3, 126.7 (dd, J FC = 5.9, 3.5 Hz), 119.9 (d, J FC = 19.1 Hz), 117.1 (d, J FC = 17.1 Hz), 58.0, 44.7.

[0124] 19 F NMR (376 MHz, CD3OD) δ -140.7, -142.9.

[0125] ESIHRMS: m / z Calcd. For C 16 H 12 F2O4: (M+Na) + 329.0596. Found: 329.0587.

[0126] Product 2j: 2-Phenyl-2-(dibenzo[b,d]furan-2-yl)succinic acid (2j), 2-(dibenzo[b,d]furan-2-yl)-2-phenylsuccinic acid

[0127]

[0128] 60.5 mg, white solid, yield: 84%.

[0129] 1 H NMR (400 MHz, CD3OD) δ 8.00 - 7.88 (m, 2H), 7.49 - 7.23 (m, 10H), 3.94 (dd, J = 16.8, 3.2 Hz, 1H), 3.87 - 3.73 (m, 1H).

[0130] 13 C NMR (100 MHz, CD3OD) δ 176.8, 175.0, 156.9, 155.1, 142.0, 129.5, 129.2, 129.0(4), 129.0(1), 128.2, 125.8, 125.2, 123.9, 123.3, 121.6, 120.8, 112.4, 57.7, 42.4.

[0131] ESIHRMS: m / z Calcd. For C 22 H 16 O5: (M+Na) + 383.0890. Found: 383.0878.

[0132] Product 2k: 2-Phenyl-2-(naphthalen-2-yl)succinic acid (2k), 2-(naphthalen-2-yl)-2-phenylsuccinic acid

[0133]

[0134] 53.0 mg, white solid, yield: 83%.

[0135] 1 H NMR (400 MHz, CD3OD) δ 7.93 (d, J = 1.6 Hz, 1H), 7.79 (dt, J = 6.0, 3.2 Hz, 2H), 7.70 (d, J = 8.8 Hz, 1H), 7.50 - 7.41 (m, 2H), 7.39 - 7.18 (m, 6H), 3.60 (d, J = 7.2 Hz, 2H).

[0136] 1313C NMR (100 MHz, CD3OD) δ 176.5, 174.3, 144.4, 141.7, 134.3, 133.6, 130.0, 129.3, 128.9, 128.5, 128.3, 128.2, 127.9, 127.2, 127.1, 58.6, 44.7.

[0137] ESIHRMS: m / z Calcd. For C 20 H 16 O4: (M + Na) + 343.0941. Found: 343.0934.

[0138] Product 21: 2-(4-fluorophenyl)-2-(4-methoxyphenyl)succinic acid (21), 2-(4-fluorophenyl)-2-(4-methoxyphenyl)succinic acid

[0139]

[0140] 52.0 mg, white solid, yield: 82%.

[0141] 1 1H NMR (400 MHz, CD3OD) δ 7.18 (dd, J = 8.8, 5.2 Hz, 2H), 7.10 (d, J = 8.8 Hz, 2H), 6.86 (t, J = 8.8 Hz, 2H), 6.73 (d, J = 8.8 Hz, 2H), 3.66 (s, 3H), 3.33 (q, J = 16.0 Hz, 2H).

[0142] 13 13C NMR (100 MHz, CD3OD) δ 177.3, 174.7, 162.8 (d, J FC = 243.4 Hz), 159.9, 140.9 (d, J FC = 2.8 Hz), 136.3, 131.9 (d, J FC = 8.0 Hz), 130.7, 115.1 (d, J FC = 21.2 Hz), 114.3, 57.7, 55.7, 45.3.

[0143] 19 19F NMR (376 MHz, CD3OD) δ -118.0.

[0144] ESIHRMS: m / z Calcd. For C 17 H 15 FO5: (M + Na)+ 341.0796. Found: 341.0798.

[0145] Product 2m: 2,2-bis(4-fluorophenyl)succinic acid (2m), 2,2-bis(4-fluorophenyl)succinic acid

[0146]

[0147] 43.8 mg, white solid, yield: 72%.

[0148] 1 H NMR (400 MHz, CD3OD) δ 7.40 - 7.26 (m, 4H), 7.07 - 6.92 (m, 4H), 3.46 (d, J = 3.6 Hz, 2H).

[0149] 13 C NMR (100 MHz, CD3OD) δ 176.5, 174.2, 164.3 (d, J FC = 243.8 Hz), 140.5 (d, J FC = 2.8 Hz), 131.9 (d, J FC = 7.9 Hz), 115.4 (d, J FC = 21.5 Hz), 57.7, 45.0.

[0150] 19 F NMR (376 MHz, CD3OD) δ -117.7.

[0151] ESIHRMS: m / z Ca;cd. For C 16 H 12 F2O4: (M+Na) + 329.0596. Found: 329.0585.

[0152] Product 2n: 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid (2n), 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid

[0153]

[0154] White solid, 22.2 mg, yield: 50%, d.r. = 9:1.

[0155] 11H NMR (400 MHz, CD3OD) δ 7.40 - 7.22 (m, 1H), 7.09 - 7.03 (m, 3H), 4.06 (dd, J = 39.2, 6.8 Hz, 1H), 3.09 (ddd, J = 10.4, 8.4, 3.6 Hz, 1H), 2.87 - 2.73 (m, 2H), 2.26 - 2.17 (m, 1H), 1.81 (dddd, J = 13.2, 10.0, 9.2, 6.0 Hz, 1H).

[0156] 13 13C NMR (100 MHz, CD3OD) δ 177.7, 177.4, 137.4, 133.5, 130.1, 129.3, 127.9, 127.1, 48.5, 44.2, 29.3, 25.6.

[0157] ESIHRMS: m / z Calcd. For C 12 H 12 O4: (M + Na) + 243.0628. Found: 243.0628.

[0158] Product 2o: 2-([1,1'-biphenyl]-4-yl)-3-methylsuccinic acid (2o)

[0159]

[0160] 28.5 mg, white solid, yield: 50%, d.r. = 2.4:1.

[0161] 1 1H NMR (400 MHz, CD3OD) δ 7.62 - 7.52 (m, 4H), 7.46 - 7.37 (m, 4H), 7.35 - 7.27 (m, 1H), 3.77 (t, J = 11.2 Hz, 1H), 3.27 - 3.08 (m, 1H), 1.35 (d, J = 6.8 Hz, 2.12H), 1.00 (d, J = 7.2 Hz, 0.88H).

[0162] 1313C NMR (100 MHz, CD3OD) δ 179.5, 178.0, 176.8, 175.8, 141.9, 141.8, 141.7, 137.9, 137.4, 130.0 (4), 130.0 (1), 129.9, 129.8, 128.4 (3), 128.3 (8), 128.3 (6), 128.0, 127.9, 56.0, 55.4, 44.7, 43.7, 17.1, 16.0.

[0163] ESI HRMS: m / z Calcd. For C 17 H 16 O4: (M + Na) + 307.0941. Found: 307.0941.

[0164] Product 2p: 2,2 - bis(4 - fluorophenyl)-3 - methylsuccinic acid (2p)

[0165]

[0166] 55.1 mg, white solid, yield: 86%.

[0167] 1 1H NMR (400 MHz, CD3OD) δ 7.43 - 7.30 (m, 4H), 7.00 (dt, J = 31.2, 8.0 Hz, 4H), 4.06 (q, J = 6.8 Hz, 1H), 1.16 (d, J = 6.8 Hz, 3H).

[0168] 13 13C NMR (100 MHz, CD3OD) δ 178.0, 177.1, 163.1 (d, J FC = 244.2 Hz), 162.9 (d, J FC = 243.7 Hz), 139.1, 137.9, 134.1 (d, J FC = 7.8 Hz), 132.4 (d, J FC = 7.9 Hz), 115.5 (d, J FC = 21.4 Hz), 114.5 (d, J FC = 22.1 Hz), 62.7, 45.9, 15.2.

[0169] 19 19F NMR (376 MHz, CD3OD) δ - 117.8, - 118.5.

[0170] ESIHRMS: m / z Calcd. For C 17 H 14 F2O4: (M+Na) + 343.0952. Found: 343.0945.

[0171] Product 2q: 3-methyl-2-phenyl-2-(m-tolyl)succinic acid (2q), 3-methyl-2-phenyl-2-(m-tolyl)succinic acid

[0172]

[0173] 47.7 mg, white solid, yield: 80%, d.r. = 1:1.

[0174] 1 H NMR (400 MHz, CD3OD) δ 7.38 (dd, J = 8.4, 1.2 Hz, 1H), 7.31 - 6.99 (m, 8H), 3.98 (qd, J = 7.2, 4.0 Hz, 1H), 2.27 (d, J = 11.2 Hz, 3H), 1.24 - 1.19 (m, 3H).

[0175] 13 C NMR (100 MHz, CD3OD) δ 179.2, 179.1, 177.8(0), 177.7(7), 143.7, 143.6, 142.7, 142.5, 138.6, 137.4, 132.6, 132.1, 130.9, 130.4, 128.9, 128.8, 128.7, 128.2, 127.9(2), 127.8(5), 127.5, 127.2, 64.0, 63.9(5), 46.8, 46.8, 21.7, 21.6, 15.6, 15.5.

[0176] ESIHRMS: m / z Calcd. For C 18 H 18 O4: (M+Na) + 321.1097. Found: 321.1089.

[0177] Product 2r: 3-methyl-2,2-diphenylsuccinic acid (2r), 3-methyl-2,2-diphenylsuccinic acid

[0178]

[0179] 41.2 mg, white solid, yield: 73%.

[0180] 1 1H NMR (400 MHz, CD3OD) δ 7.41 - 7.18 (m, 10H), 4.09 (qd, J = 6.8, 2.4 Hz, 1H), 1.22 - 1.10 (m, 3H).

[0181] 13 13C NMR (100 MHz, CD3OD) δ 178.3, 177.4, 143.3, 142.1, 132.3, 130.5, 128.8, 128.0, 127.9, 127.6, 63.7, 45.8, 15.3.

[0182] ESIHRMS: m / z Calcd. For C 17 H 16 O4: (M+Na) + 307.0941. Found: 307.0932.

[0183] Product 2s: (2s)-2,2,3-triphenylsuccinic acid

[0184]

[0185] 61.4 mg, white solid, yield: 89%.

[0186] 1 1H NMR (400 MHz, CD3OD) δ 7.45 - 7.35 (m, 2H), 7.22 (d, J = 5.2 Hz, 3H), 7.09 (ddt, J = 20.0, 15.2, 7.6 Hz, 8H), 6.90 (d, J = 7.6 Hz, 2H), 5.21 (s, 1H).

[0187] 13 13C NMR (100 MHz, CD3OD) δ 177.2, 176.9, 142.6, 141.8, 137.5, 132.1, 131.9, 131.5, 128.6, 128.3, 128.2, 128.1, 127.6, 66.1, 58.9.

[0188] ESIHRMS: m / z Calcd. For C 22 H 18 O4: (M+Na) + 321.1097. Found: 321.1095.

[0189] Example 2

[0190] A method for preparing dicarboxylic acid compounds using 1,3-diene compounds as reaction substrates includes the following steps:

[0191] (1) Add 0.2 mmol of the reaction substrate (the reaction substrate and the reaction formula are shown in Table 2) and 0.004 mmol of the photosensitizer catalyst 4DPAIPN (2 mol%) to a dry reaction tube (2 mL) containing a magnetic stir bar.

[0192] (2) Transfer the Schlenk tube into the glove box, and add 0.4 mmol of [N(nBu)4]2C2O4 (229.2 mg, 0.4 mmol, 2 equivalents) and 1.0 mmol of CsF (151.9 mg, 1.0 mmol, 5 equivalents) to the reaction tube.

[0193] (3) After sealing the reaction tube, take it out of the glove box and connect it to a double manifold connected to an N2 cylinder. Loosen the lid and evacuate and refill with N2 on the double manifold at least 3 times.

[0194] (4) Add 1.5 mL of the solvent DMF to the reaction tube filled with N2.

[0195] (5) Place the reaction tube containing the reaction solution 1 - 2 cm away from a 30 W blue LED lamp (wavelength around 420 nm), and stir and react at room temperature (around 25 °C) for 8 - 24 hours.

[0196] (6) Quench the reaction with 3 mL of 1 N hydrochloric acid; extract with ethyl acetate, dry over Na2SO4, and concentrate and evaporate the quenched reactant to dryness on a rotary evaporator. Purify the residue by flash column chromatography. The purification conditions are: first rinse with a mixture of petroleum ether / ethyl acetate = 10 / 1 (v / v), then rinse with a mixture of petroleum ether / ethyl acetate = 5 / 1 (v / v), and finally elute with a mixture of petroleum ether / ethyl acetate = 1 / 2 (v / v) to obtain the pure product.

[0197] Table 2 1,3-diene compounds as substrates, their corresponding products, and yields

[0198]

[0199] Performance characterization:

[0200] Among them, product 4a: 2-(2,2-diphenylallyl)succinic acid (4a), 2-(2,2-diphenylvinyl)succinic acid

[0201]

[0202] 46.3 mg, white solid, yield: 74%.

[0203] 1 1H NMR (400 MHz, CD3OD) δ 7.42 - 7.32 (m, 3H), 7.26 - 7.17 (m, 7H), 6.04 (d, J = 10.4 Hz, 1H), 3.57 (ddd, J = 10.4, 8.4, 5.6 Hz, 1H), 2.78 (dd, J = 16.4, 8.4 Hz, 1H), 2.51 (dd, J = 16.4, 5.6 Hz, 1H).

[0204] 13 13C NMR (100 MHz, CD3OD) δ 176.7, 174.9, 146.4, 143.2, 140.5, 130.8, 129.4, 129.2, 128.6, 128.4, 126.0, 43.6, 37.8.

[0205] ESI HRMS: m / z Calcd. For C 18 H 16 O4: (M + Na) + 319.0941. Found: 319.0941.

[0206] Product 4b: 2-(2-Phenyl-2-(3-methylphenyl)allyl)succinic acid (4b), 2-(2-phenyl-2-(m-tolyl)vinyl)succinic acid

[0207]

[0208] 42 mg, white solid, yield: 68%, E:Z = 1.2:1.

[0209] 1 1H NMR (400 MHz, CD3OD) δ 7.41 - 7.11 (m, 7H), 7.01 (dd, J = 22.4, 8.0 Hz, 2H), 6.02 (ddd, J = 10.4, 5.2, 2.0 Hz, 1H), 3.62 - 3.51 (m, 1H), 2.78 (ddd, J = 16.0, 8.0, 5.2 Hz, 1H), 2.53 (t, J = 4.8 Hz, 0.55H), 2.49 (t, J = 4.8 Hz, 0.45H), 2.35 (d, J = 4.8 Hz, 1.38H), 2.26 (d, J = 4.8 Hz, 1.62H).

[0210] 1313C NMR (100 MHz, CD3OD) δ 176.7 (9), 176.7 (6), 174.9, 146.5, 143.3, 143.2, 140.7, 140.5, 139.2, 138.9, 131.4, 130.8, 129.4, 129.3 (2), 129.2 (6), 129.2, 129.1, 129.0, 128.6, 128.4, 127.9, 125.9, 125.7, 43.6 (2), 43.6 (1), 37.8 (9), 37.8 (7), 21.5 (0), 21.4 (5).

[0211] ESI HRMS: m / z Calcd. For C 19 H 18 O4: (M + Na) + 333.1097. Found: 333.1093.

[0212] Product 4c: 2-(2-Phenyl-2-(4-methylphenyl)allyl)succinic acid (4c), 2-(2-phenyl-2-(p-tolyl)vinyl)succinic acid

[0213]

[0214] 47.8 mg, white solid, yield: 77%, E:Z = 1.3:1.

[0215] 1 1H NMR (400 MHz, CD3OD) δ 7.43 - 7.33 (m, 1H), 7.30 - 7.09 (m, 7H), 7.07 (s, 1H), 6.00 (d, J = 10.6 Hz, 1H), 3.56 (m, 1H), 2.77 (ddd, J = 16.4, 8.4, 2.0 Hz, 1H), 2.51 (dd, J = 5.6, 2.4 Hz, 0.56H), 2.47 (dd, J = 5.6, 2.4 Hz, 0.42H), 2.37 (s, 1.71H), 2.29 (s, 1.27H).

[0216] 13 13C NMR (100 MHz, CD3OD) δ 176.8, 175.0, 146.4, 146.3, 143.4, 140.7, 140.4, 138.5 (4), 138.4 (6), 137.6, 130.9, 130.8, 130.0, 129.8, 129.4, 129.2, 128.6, 128.5, 128.3, 125.9, 125.2, 43.7, 37.9, 21.3, 21.1.

[0217] ESIHRMS: m / z Calcd. For C 19 H 18 O4: (M+Na) + 333.1097. Found: 333.1093.

[0218] Product 4d: 2-(2-phenyl-2-([1,1'-biphenyl]-4-yl)allyl)succinic acid (4d), 2-(2-([1,1'-biphenyl]-4-yl)-2-phenylvinyl)succinic acid

[0219]

[0220] 51.4 mg, white solid, yield: 69%, E:Z = 1:1.

[0221] 1 H NMR (400 MHz, CD3OD) δ 7.66 - 7.24 (m, 14H), 6.12 (d, J = 10.4 Hz, 0.5H), 6.06 (d, J = 10.4 Hz, 0.5H), 3.63 (dq, J = 33.2, 8.4 Hz, 1H), 2.81 (dt, J = 15.6, 7.2 Hz, 1H), 2.54 (ddd, J = 15.6, 8.8, 5.6 Hz, 1H).

[0222] 13 C NMR (100 MHz, CD3OD) δ 175.6, 175.6, 173.9, 173.8, 145.1, 144.9, 142.3, 141.1, 141.0, 140.8, 140.7, 140.6, 139.5, 138.6, 130.4, 129.9, 128.9, 128.8, 128.5, 128.2, 127.9, 127.7, 127.5, 127.4, 127.4, 127.0, 126.8, 126.7, 125.3, 125.0, 42.8(4), 42.8(0), 34.0, 36.9.

[0223] ESIHRMS: m / z Calcd. For C 24 H 20 O4: (M+Na) + 395.1254. Found: 395.1251.

[0224] Product 4e: 2-(2-Phenyl-2-(4-fluorophenyl)allyl)succinic acid (4e), 2-(2-(4-fluorophenyl)-2-phenylvinyl)succinic acid

[0225]

[0226] 45.3 mg, white solid, yield: 72%, E:Z = 1.3:1.

[0227] 1 H NMR (400 MHz, CD3OD) δ 7.39 (m, 1H), 7.21 (m, 7H), 6.99 (m, 1H), 6.12 - 5.93 (m, 1H), 3.56 (m, 1H), 2.79 (dt, J = 15.6, 7.2 Hz, 1H), 2.54 (m, 0.56H), 2.50 (m, 0.42H).

[0228] 13 C NMR (100 MHz, CD3OD) δ 176.6, 176.5, 174.9, 163.8 (d, J FC = 244.5 Hz), 163.6 (d, J FC = 244.1 Hz), 145.4, 145.3, 143.1, 140.3, 139.5 (d, J FC = 3.1 Hz), 136.6 (d, J FC = 3.1 Hz), 132.8 (d, J FC = 8.1 Hz), 130.9, 130.8, 130.2 (d, J FC = 8.1 Hz), 129.5, 129.3, 128.8, 128.4, 126.6, 126.2, 116.2 (d, J FC = 23.4 Hz), 115.9 (d, J FC = 21.7 Hz), 43.6 (6), 43.6 (5), 37.8 (1), 37.7 (6).

[0229] 19 F NMR (376 MHz, CD3OD) δ -116.1, -116.5.

[0230] ESIHRMS: m / z Calcd. For C 18 H 15 (M + Na) + 337.0847. Found: 337.0846.

[0231] Product 4f: 2-(2,2-bis(4-fluorophenyl)vinyl)succinic acid (4f), 2-(2,2-bis(4-fluorophenyl)vinyl)succinic acid

[0232]

[0233] 54.5 mg, white solid, yield: 82%.

[0234] 1 1H NMR (400 MHz, CD3OD) δ 7.11 (ddt, J = 31.2, 17.2, 7.2 Hz, 6H), 6.90 (t, J = 8.4 Hz, 2H), 5.91 (d, J = 10.4 Hz, 1H), 3.43 (dt, J = 10.4, 6.8 Hz, 1H), 2.68 (dd, J = 16.4, 8.0 Hz, 1H), 2.42 (dd, J = 16.4, 5.6 Hz, 1H).

[0235] 13 13C NMR (100 MHz, CD3OD) δ 176.5, 174.9, 163.8 (d, J FC = 244.6 Hz), 163.7 (d, J FC = 244.2 Hz), 144.3, 139.4 (d, J FC = 2.8 Hz), 136.4 (d, J FC = 3.0 Hz), 132.8 (d, J FC = 7.9 Hz), 130.2 (d, J FC = 8.1 Hz), 126.7, 116.3 (d, J FC = 31.5 Hz), 116.0 (d, J FC = 31.5 Hz), 43.7, 37.7.

[0236] 19 19F NMR (376 MHz, CD3OD) δ -116.2, -116.6.

[0237] ESIHRMS: m / z Calcd. For C 18 H 14 F2O4: (M+Na) + 55.0752. Found: 355.0751.

[0238] Product 4g: (E)-2-phenylhex-3-enedioic acid (4g), (E)-2-phenylhex-3-enedioic acid

[0239]

[0240] 19.4 mg, clear liquid, yield: 44%, E∶Z > 20∶1.

[0241] 1 H NMR (400 MHz, CD3OD) δ 7.31 (d, J = 4.4 Hz, 4H), 7.26 - 7.22 (m, 1H), 5.99 (dd, J = 15.6, 8.4 Hz, 1H), 5.69 (dt, J = 14.8, 7.2 Hz, 1H), 4.30 (d, J = 8.4 Hz, 1H), 3.08 (d, J = 7.2 Hz, 2H).

[0242] 13 C NMR (100 MHz, CD3OD) δ 176.1, 175.3, 140.2, 132.8, 129.6, 129.0, 128.2, 126.4, 55.9, 38.4.

[0243] ESIHRMS: m / z Calcd. For C 12 H 12 O4: (M+Na) + 243.0628. Found: 243.0629.

[0244] Product 4h: (E)-2-phenyl-2-propylhex-3-enedioic acid (4h)

[0245]

[0246] 35.3 mg, clear liquid, yield: 67%, E∶Z > 20∶1.

[0247] 1 H NMR (400 MHz, CD3OD) δ 7.31 - 7.20 (m, 5H), 6.15 (d, J = 16.0 Hz, 1H), 5.53 (dt, J = 16.0, 7.2 Hz, 1H), 3.11 (d, J = 7.2 Hz, 2H), 2.15 - 1.98 (m, 2H), 1.30 - 1.18 (m, 2H), 0.90 (t, J = 7.2 Hz, 3H).

[0248] 1313C NMR (100 MHz, CD3OD) δ 178.0, 175.5, 144.0, 137.1, 129.2, 128.4, 127.7, 125.0, 58.1, 40.6, 38.9, 19.3, 14.9.

[0249] ESIHRMS: m / z Calcd. For C 15 H 18 O4: (M+Na) + 285.1097. Found: 285.1099.

[0250] Product 4i: 4-methyl-2-phenylhex-3-enedioic acid (4i)

[0251]

[0252] 26.1 mg, white solid, yield: 56%, E:Z = 8:1.

[0253] 1 1H NMR (400 MHz, CD3OD) δ 7.30 (dd, J = 14.0, 6.4 Hz, 4H), 7.22 (t, J = 7.2 Hz, 1H), 5.82 (d, J = 9.2 Hz, 1H), 4.53 (d, J = 9.6 Hz, 1H), 3.10 (s, 0.22H), 3.06 (s, 1.77H), 1.86 (s, 0.33H), 1.75 (s, 2.65H).

[0254] 13 13C NMR (100 MHz, CD3OD) δ 176.4, 175.3, 140.7, 133.1, 129.6, 128.9, 128.1, 127.8, 51.6, 45.6, 16.8.

[0255] ESIHRMS: m / z Calcd. For C 13 H 14 O4: (M+Na) + 257.0784. Found: 257.0782.

[0256] Product 4j: (E)-2-methyl-5-phenylhex-3-enedioic acid (4j)

[0257]

[0258] 17.1 mg, white solid, yield: 36%, E:Z > 20:1.

[0259] 1 H NMR (400 MHz, CD3OD) δ 7.27 (dt, J = 23.6, 2.4 Hz, 5H), 5.99 (dd, J = 15.6, 8.4 Hz, 1H), 5.69 (dd, J = 15.6, 7.6 Hz, 1H), 4.34 - 4.25 (m, 1H), 3.15 (p, J = 6.8 Hz, 1H), 1.23 (ddd, J = 13.2, 7.2, 2.4 Hz, 3H).

[0260] 13 C NMR (100 MHz, CD3OD) δ 178.2, 176.1, 140.2, 133.2, 130.7, 129.6, 129.0, 128.2, 55.8, 43.8, 17.6.

[0261] ESIHRMS: m / z Calcd. For C 13 H 14 O4: (M+Na) + 257.0784. Found: 257.0784.

[0262] Product 4k: (E)-2-([1,1′-biphenyl]-4-yl)hex-3-enedioic acid (4k)

[0263]

[0264] 24.4 mg, white solid, yield: 41%, E:Z > 20:1.

[0265] 1 H NMR (400 MHz, CD3OD) δ 7.58 (t, J = 8.0 Hz, 4H), 7.40 (dd, J = 8.0, 5.6 Hz, 4H), 7.31 (t, J = 7.2 Hz, 1H), 6.03 (dd, J = 15.6, 8.4 Hz, 1H), 5.73 (dt, J = 14.8, 6.8 Hz, 1H), 4.36 (d, J = 8.4 Hz, 1H), 3.10 (d, J = 7.2 Hz, 2H).

[0266] 1313C NMR (100 MHz, CD3OD) δ 176.1, 175.4, 142.0, 141.4, 139.3, 132.7, 129.8, 129.5, 128.3, 128.2, 127.9, 126.5, 55.6, 38.5.

[0267] ESIHRMS: m / z Calcd. For C 18 H 16 O4: (M + Na) + 319.0941. Found: 319.0931.

[0268] Product 4l: (E)-2-(4-fluorophenyl)hex-3-enedioic acid

[0269]

[0270] 10.2 mg, clear liquid, yield: 21%, E:Z > 20:1.

[0271] 1 1H NMR (400 MHz, CD3OD) δ 7.38 - 7.28 (m, 2H), 7.05 (td, J = 8.8, 1.6 Hz, 2H), 6.05 - 5.91 (m, 1H), 5.76 - 5.63 (m, 1H), 4.32 (d, J = 8.0 Hz, 1H), 3.09 (d, J = 6.8 Hz, 2H).

[0272] 13 13C NMR (100 MHz, CD3OD) δ 175.9, 175.3, 163.4 (d, J FC = 242.6 Hz), 136.2 (d, J FC = 1.7 Hz), 132.6, 130.9 (d, J FC = 8.0 Hz), 126.7, 116.2 (d, J FC = 21.6 Hz), 55.0, 38.4.

[0273] 19 19F NMR (376 MHz, CD3OD) δ -118.0.

[0274] ESIHRMS: m / z Calcd. For C 12 H 11 FO4: (M + Na) + 261.0534. Found: 261.0529.

[0275] Example 3

[0276] A method for preparing dicarboxylic acid compounds using N-Boc substituted indole compounds as reaction substrates comprises the following steps:

[0277] (1) Add 0.2 mmol of the reaction substrate (the reaction substrate and the reaction formula are shown in Table 3) and 0.004 mmol of the photosensitizer catalyst 4DPAIPN (2 mol%) to a dry reaction tube (2 mL) containing a magnetic stirrer bar.

[0278] (2) Transfer the Schlenk tube into the glove box and charge 0.4 mmol of [N(nBu)4]2C2O4 (229.2 mg, 0.4 mmol, 2 equivalents) and 1.6 mmol of CsF (1.6 mmol, 8 equivalents) into the reaction tube.

[0279] (3) After sealing the reaction tube, take it out of the glove box and connect it to a double manifold connected to an N2 cylinder. Loosen the lid and evacuate and refill with N2 on the double manifold at least 3 times.

[0280] (4) Add 1.5 mL of the solvent DMF to the reaction tube filled with N2.

[0281] (5) Place the reaction tube containing the reaction solution 1 - 2 cm away from a 30 W blue LED lamp (with a wavelength of about 420 nm) and stir the reaction at room temperature (about 25 °C) for 8 - 24 hours.

[0282] (6) Quench the reaction with 3 mL of 1 N hydrochloric acid; extract with ethyl acetate, dry over Na2SO4, and concentrate and evaporate the quenched reactant to dryness on a rotary evaporator. Purify the residue by flash column chromatography under the following conditions: first rinse with a mixture of petroleum ether / ethyl acetate = 10 / 1 (v / v), then rinse with a mixture of petroleum ether / ethyl acetate = 5 / 1 (v / v), and finally elute with a mixture of petroleum ether / ethyl acetate = 1 / 2 (v / v) to obtain the pure product.

[0283] Table 3 N-Boc substituted indole compounds as substrates, their corresponding products, and yields

[0284]

[0285] Performance characterization:

[0286] Among them, product 6a: (2S,3S)-1-(tert-butoxycarbonyl)indoline-2,3-dicarboxylic acid (6a), (2S,3S)-1-(tert-butoxycarbonyl)indoline-2,3-dicarboxylic acid

[0287]

[0288] 36.7 mg, white solid, yield: 60%, d.r. > 20:1.

[0289] 1 H NMR (400 MHz, CD3OD) δ 7.83 (brs, 1H), 7.40 (dd, J = 7.2, 4.0 Hz, 1H), 7.26 (q, J = 7.6 Hz, 1H), 7.01 (dp, J = 12.8, 5.2 Hz, 1H), 5.21 (s, 1H), 4.18 (s, 1H), 1.53 (s, 9H).

[0290] 13 C NMR (100 MHz, CD3OD) δ 174.2, 173.3, 153.0, 143.4, 130.1, 127.8, 126.3, 123.9, 115.5, 82.8, 64.3, 51.2, 28.5.

[0291] ESIHRMS: m / z Calcd.For C 15 H 17 NO6: (M+Na) + 330.0948. Found: 330.0944.

[0292] Product 6b: (2S,3S)-1-(tert-butoxycarbonyl)-4-fluoroindoline-2,3-dicarboxylic acid (6b), (2S,3S)-1-(tert-butoxycarbonyl)-4-fluoroindoline-2,3-dicarboxylic acid

[0293]

[0294] 28.7 mg, white solid, yield: 44%, d.r. > 20:1.

[0295] 1 H NMR (400 MHz, DMSO-d6) δ 7.75 - 7.48 (m, 1H), 7.33 (q, J = 8.0 Hz, 1H), 6.85 (t, J = 8.8 Hz, 1H), 4.98 (s, 1H), 4.30 - 4.19 (m, 1H), 1.49 (brs, 9H).

[0296] 13 C NMR (100 MHz, DMSO-d6) δ 171.3, 171.1, 158.7 (d, J FC=245.4Hz), 150.7, 144.8, 131.4 (d, J FC =8.1Hz), 113.3(d, J FC =20.7Hz), 110.1, 109.7 (d, J FC =19.8Hz), 81.4, 64.1, 46.6, 27.7.

[0297] 19 F NMR (376MHz, CD3OD) δ-119.2.

[0298] ESIHRMS: m / z Calcd.For C 15 H 16 FNO6: (M+Na) + 348.0854.Found:348.0851.

[0299] Product 6c: (2S,3S)-1-(tert-butoxycarbonyl)-5-fluoroindoline-2,3-dicarboxylic acid (6c), (2S,3S)-1-(tert-butoxycarbonyl)-5-fluoroindoline-2,3-dicarboxylic acid

[0300]

[0301] 49.2 mg, white solid, yield: 76%, dr>20:1.

[0302] 1 H NMR (400MHz, CD3OD) δ7.80 (brs, 1H), 7.20-7.09 (m, 1H), 7.06-6.95 (m, 1H), 5.23 (s, 1H), 4.21 (s, 1H), 1.51 (brs, 9H).

[0303] 13 C NMR (100MHz, CD3OD) δ172.3, 171.0, 158.4 (d, J FC =238.7Hz), 151.3, 138.1, 128.0 (d, J FC =7.4Hz), 114.8, 114.6, 112.0 (d, J FC =24.7Hz), 81.2, 62.9, 49.2, 26.8.

[0304] 19 F NMR (376MHz, CD3OD) δ-123.0.

[0305] ESIHRMS: m / z Calcd. For C 15 H 16 FNO6: (M+Na) + 348.0854. Found: 348.0851.

[0306] Product 6d: (2S,3S)-1-(tert-butoxycarbonyl)-7-fluoroindoline-2,3-dicarboxylic acid (6d), 1-(tert-butoxycarbonyl)-7-fluoroindoline-2,3-dicarboxylic acid

[0307]

[0308] 32.1 mg, white solid, yield: 49%, d.r. > 20:1.

[0309] 1 H NMR (400 MHz, CD3OD) δ 7.24 (d, J = 5.2 Hz, 1H), 7.08 (tp, J = 8.0, 4.4 Hz, 2H), 5.37 (dd, J = 4.0, 2.4 Hz, 1H), 4.18 (s, 1H), 1.56 - 1.50 (m, 9H).

[0310] 13 C NMR (100 MHz, CD30D) δ 173.7, 172.9, 153.9, 152.4 (d, J FC = 250.6 Hz), 133.8, 129.9 (d, J FC = 10.8 Hz), 126.6 (d, J FC = 6.0 Hz), 122.3 (d, J FC = 3.1 Hz), 118.2 (d, J FC = 21.2 Hz), 83.4, 66.3, 51.8, 28.3.

[0311] 19 F NMR (376 MHz, CD3OD) δ -118.3.

[0312] ESIHRMS: m / z Calcd. For C 15 H 16 FNO6: (M+Na) + 348.0854. Found: 348.0854.

[0313] Product 6e: (2S,3S)-1-(tert-butoxycarbonyl)-6-(methoxycarbonyl)indoline-2,3-dicarboxylic acid (6e), (2S,3S)-1-(tert-butoxycarbonyl)-6-(methoxycarbonyl)indoline-2,3-dicarboxylic acid

[0314]

[0315] 39.4 mg, white solid, yield: 54%, d.r. > 20:1.

[0316] 1 H NMR (400 MHz, CD3OD) δ 8.35 (brs, 1H), 7.70 (q, J = 6.8 Hz, 1H), 7.51 (q, J = 6.8 Hz, 1H), 5.25 (s, 1H), 4.28 (s, 1H), 3.34 (s, 3H), 1.59 (brs, 9H).

[0317] 13 C NMR (100 MHz, CD3OD) δ 173.8, 172.5, 168.2, 152.9, 144.0, 133.2, 132.3, 126.5, 125.4, 116.2, 83.2, 64.5, 52.7, 51.2, 28.4.

[0318] ESIHRMS: m / z Calcd.For C 17 H 19 NO8: (M+Na) + 388.1003. Found: 388.1002.

[0319] Product 6f: (2S,3S)-1-(tert-butoxycarbonyl)-6-(methyl)indoline-2,3-dicarboxylic acid (6f), (2S,3S)-1-(tert-butoxycarbonyl)-6-(methyl)indoline-2,3-dicarboxylic acid

[0320]

[0321] 42.0 mg, white solid, yield: 65%, d.r. > 20:1.

[0322] 11H NMR (400 MHz, CD3OD) δ 7.68 (brs, 1H), 7.26 (d, J = 7.6 Hz, 1H), 6.83 (d, J = 7.6 Hz, 1H), 5.19 (s, 1H), 4.14 - 4.07 (m, 1H), 2.33 (s, 3H), 1.52 (brs, 9H).

[0323] 13 13C NMR (100 MHz, CD3OD) δ 174.3, 173.5, 153.0, 143.5, 140.4, 125.9, 125.0, 124.5, 116.2, 82.7, 64.6, 50.9, 28.5, 21.8.

[0324] ESIHRMS: m / z Calcd. For C 17 H 19 NO8: (M + Na) + 344.1105. Found: 344.1106.

[0325] Product 6g: (2S,3S)-1-(tert-butoxycarbonyl)-2-phenylindoline-2,3-dicarboxylic acid (6g)

[0326]

[0327] 31.9 mg, white solid, yield: 42%, d.r. > 20:1.

[0328] 1 1H NMR (400 MHz, CD3OD) δ 7.95 (d, J = 7.6 Hz, 1H), 7.58 (dd, J = 6.4, 3.2 Hz, 2H), 7.29 (t, J = 7.6 Hz, 1H), 7.25 - 7.17 (m, 4H), 7.03 (t, J = 7.6 Hz, 1H), 4.83 (s, 1H), 1.24 (s, 9H).

[0329] 13 13C NMR (100 MHz, CD3OD) δ 174.4, 172.5, 153.4, 145.0, 138.8, 129.7, 128.9, 128.6, 128.3, 127.3, 127.2, 124.0, 115.5, 83.0, 76.6, 60.2, 28.2.

[0330] ESIHRMS: m / z Calcd. For C21 H 21 NO6: (M+Na) + 406.1261.Found:406.1255.

[0331] Product 6h: (2S,3S)-1-(tert-butoxycarbonyl)-3-methylindoline-2,3-dicarboxylic acid (6h), (2S,3S)-1-(tert-butoxycarbonyl)-3-methylindoline-2,3-dicarboxylic acid

[0332]

[0333] 44.2 mg, white solid, yield: 69%, dr>20:1.

[0334] 1 H NMR (400MHz, CD3OD) δ7.87-7.43 (m, 1H), 7.32 (d, J=7.6Hz, 1H), 7.25 (t, J=7.6Hz, 1H), 7.05-6.96 (m, 1H), 5.37 (s, 1H), 1.61 (s, 3H), 1.52 (s, 9H).

[0335] 13 C NMR (100MHz, CD3OD) δ176.0, 172.9, 153.0, 143.2, 133.6, 130.1, 125.1, 123.9, 115.2, 82.9, 69.4, 53.6, 28.5, 20.9.

[0336] ESIHRMS: m / z Calcd.For C 16 H 19 NO6: (M+Na) + 344.1105.Found:344.1106.

[0337] Example 4

[0338] The method for preparing a dicarboxylic acid compound using 1,1-diphenylene as a reaction substrate comprises the following steps:

[0339] (1) 0.2 mmol of 1,1-diphenylene and 0.002 mmol of photosensitive catalyst 4CzIPN (1 mol%) were added to a dry reaction tube (2 mL) containing a magnetic rod.

[0340] (2) Transfer the Schlenk tube into the glove box, and charge 0.2 mmol of (NEt4)2C2O4 (0.2 mmol, 1 equivalent) and 1.0 mmol of Cs2CO3 (1.0 mmol, 5 equivalents) into the reaction tube.

[0341] (3) After sealing the reaction tube, take it out of the glove box and connect it to a double manifold connected to an N2 cylinder. Loosen the lid and evacuate and refill with N2 on the double manifold at least 3 times.

[0342] (4) Add 1.5 mL of the solvent DMF to the reaction tube filled with N2.

[0343] (5) Place the reaction tube containing the reaction solution 1 - 2 cm away from a 30 W blue LED lamp (with a wavelength of about 400 nm), and stir the reaction at room temperature (about 25 °C) for 24 h.

[0344] (6) Quench the reaction with 3 mL of 1 N hydrochloric acid; extract with ethyl acetate, dry over Na2SO4, and concentrate and rotary evaporate the quenched reactant to dryness. The residue is purified by flash column chromatography. The purification conditions are as follows: first rinse with a mixed solution of petroleum ether / ethyl acetate = 10 / 1 (v / v), then rinse with a mixed solution of petroleum ether / ethyl acetate = 5 / 1 (v / v), and finally elute with a mixed solution of petroleum ether / ethyl acetate = 1 / 2 (v / v) to obtain pure dibenzylidenesuccinic acid.

[0345] Example 5

[0346] A method for preparing a dicarboxylic acid compound using benzofuran as a reaction substrate comprises the following steps:

[0347] (1) Add 0.2 mmol of benzofuran and 0.03 mmol of the photosensitizer catalyst Ir[dF(CF3)ppy]2(dtbbpy)PF6 (15 mol%) to a dry reaction tube (2 mL) containing a magnetic stir bar.

[0348] (2) Transfer the Schlenk tube into the glove box, and charge 1.0 mmol of (NEt4)2C2O4 (1.0 mmol, 5 equivalents) and 1.2 mmol of KF (1.2 mmol, 6 equivalents) into the reaction tube.

[0349] (3) After sealing the reaction tube, take it out of the glove box and connect it to a double manifold connected to an N2 cylinder. Loosen the lid and evacuate and refill with N2 on the double manifold at least 3 times.

[0350] (4) Add 1.5 mL of the solvent DMF to the reaction tube filled with N2.

[0351] (5) Place the reaction tube containing the reaction solution 1 - 2 cm away from a 30 W blue LED lamp (with a wavelength of about 450 nm), and stir the reaction at room temperature (about 25 °C) for 8 h.

[0352] (6) Quench the reaction with 3 mL of 1 N hydrochloric acid; extract with ethyl acetate, dry over Na2SO4, and concentrate and rotary evaporate the quenched reactant to dryness. The residue is purified by flash column chromatography under the following conditions: first rinse with a mixture of petroleum ether / ethyl acetate = 10 / 1 (v / v), then rinse with a mixture of petroleum ether / ethyl acetate = 5 / 1 (v / v), and finally elute with a mixture of petroleum ether / ethyl acetate = 1 / 2 (v / v) to obtain the pure dihydrobenzofuran - 2,3 - dicarboxylic acid product.

[0353] In addition, the inventors of this case also referred to the foregoing embodiments and conducted tests using other raw materials, process operations, and process conditions described in this specification, and all obtained relatively ideal results.

[0354] It should be understood that the technical solutions of the present invention are not limited to the limitations of the above - mentioned specific embodiments. Any technical deformation made according to the technical solutions of the present invention without departing from the gist of the present invention and the scope protected by the claims falls within the protection scope of the present invention.

Claims

1. A method for preparing dicarboxylic acid compounds from olefins, characterized in that, Comprising: Subjecting a mixed reaction system containing an olefin compound, an inorganic base, oxalate, a photosensitive catalyst and a solvent to a light reaction to obtain a dicarboxylic acid compound; Among them, the oxalate is selected from [N( n Bu)4]2C2O4; The photosensitive catalyst is selected from 4DPAIPN; The inorganic base is selected from CsF; The olefinic compound is selected from any one of monoaryl-substituted olefinic compounds, 1,1-diarylethylene compounds, 1,3-diene compounds, N -Boc-substituted indole compounds, allene compounds, benzofuran compounds; The monoaryl-substituted olefin compound has a structure as shown in formula (I): ； Among them, R 1 is selected from alkyl, aryl, halogen, cyano or methoxy, and R 2 , R 3 are independently selected from hydrogen, alkyl or aryl; The 1,1-diarylethylene compound has a structure as shown in formula (II): ； Among them, R 4 , R 5 are independently selected from hydrogen, alkyl, methoxy or halogen, and R 6 is selected from hydrogen, alkyl or aryl; The 1,3-diene compound has a structure as shown in formula (III): ； Among them, R 7 is selected from hydrogen, alkyl, aryl or halogen, R 8 is selected from hydrogen, alkyl or aryl, R 9 , R 10 are independently selected from hydrogen or alkyl; The said N -Boc-substituted indole compounds have the structure shown in formula (IV): ； Among them, R 11 is selected from hydrogen, alkyl, aryl, halogen or ester group.

2. The method according to claim 1, wherein: The solvent is selected from any one or a combination of two or more of DMF, DMA, and DMSO.

3. The method according to claim 1, characterized in that: The molar ratio of the photosensitive catalyst to the olefin compound is 1:100 to 15:

100.

4. The method according to claim 1, wherein: The molar ratio of the oxalate to the olefin compound is 1:1 to 5:

1.

5. The method according to claim 1, wherein: The molar ratio of the inorganic base to the olefin compound is 5:1 - 8:

1.

6. The method according to claim 1, wherein Specifically including: Mixing the olefin compound, the inorganic base, the oxalate, the photosensitive catalyst and the solvent to form the mixed reaction system, and then stirring the reaction at room temperature for 8 - 24 h under a protective atmosphere and under visible light irradiation to obtain the dicarboxylic acid compound.

7. The method according to claim 6, characterized in that: The wavelength used for the visible light irradiation is 400 - 450 nm.

8. The method according to claim 6, characterized in that, Also including: After the reaction is completed, adding an inorganic acid to the obtained mixed solution for quenching reaction, and then performing separation and purification.

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