Preparation method of polysubstituted five-membered heterocyclic compound

Abstract

The invention discloses a preparation method of a multi-substituted five-membered heterocyclic compound, which comprises the following steps: mixing a photocatalyst, alkali, a compound II and a compound III in a molar ratio of (0.01-0.1): (1-2): (1-2) under an argon condition, adding a solvent, sealing, illuminating under a light source with the excitation wavelength of 390-456nm of the photocatalyst, controlling the distance between the light source and a reaction bottle to be 5-8cm, controlling the temperature to be 20-30 DEG C, continuously irradiating for 1-5 hours, and cooling to room temperature to obtain the multi-substituted five-membered heterocyclic compound. The polysubstituted five-membered heterocyclic compound is obtained; the method provided by the invention utilizes photocatalytic free radical form 3 + 2 reaction at normal temperature and pressure, can be used for later derivatization of five-membered heteroaromatic rings and sulfonamides, and has the advantages of simple and convenient synthesis process, easiness in operation, capability of remarkably improving the synthesis yield, small environmental pollution, greenness, environmental protection and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing a multi-substituted five-membered heterocyclic compound. Background Art

[0002] Five-membered heterocyclic rings containing nitrogen, oxygen, and sulfur are a very important class of compounds, which are widely present in the core structures of natural products and bioactive molecules. They have a variety of biological activities such as anti-inflammatory, anti-malarial, anti-fungal, anti-cancer, anti-hypertensive, and anti-parasitic, and are commonly used synthetic building blocks by medicinal chemists. Among the various strategies for synthesizing five-membered heterocyclic compounds, the dearomatization strategy reaction of aromatic heterocyclic compounds is an effective way to synthesize multi-substituted complex five-membered heterocyclic compounds.

[0003] The dearomatization reaction of aromatic heterocyclic compounds usually needs to overcome a high energy barrier, so it is usually necessary to produce highly active reaction intermediates in order to dearomatize with stable and inert aromatic rings. Traditional methods for producing highly active intermediates include transition metal catalysis and Lewis acid catalysis. These reactions usually require expensive transition metals or use strong Lewis acids, so there are often certain metal residues in the products, or the reaction conditions are relatively harsh, which limits the reaction substrates. In recent years, photocatalytic reactions have made great progress. Photocatalysts absorb light energy to generate excited states, which then undergo single-electron redox reactions with substrates to form highly active free radical species in a green and mild manner, providing new ideas for free radical chemistry. At present, photocatalytic reactions in the dearomatization of aromatic heterocycles mainly involve the [4+2] and [2+2] reactions of indoles, and there are few reports on the [3+2] reaction of electron-deficient five-membered aromatic heterocycles.

[0004]

[0005] The cycloaddition reactions of aminocyclopropane compounds with alkenes have been widely reported, mainly applied to electron-deficient alkenes, alkynes, strained alkenes such as pyridine and ethylene, but the [3+2] cycloaddition reactions of aromatic alkenes with aminocyclopropanes have been less reported.

[0006] The [3+2] dearomatization reaction of olefins with cyclopropylamine to synthesize five-membered carbon ring skeletons has been widely studied, but the reaction of indole with cyclopropylamine to synthesize cyclopentylamine indole through [3+2] dearomatization induced by visible light has not been reported. Visible light-mediated reactions not only overcome a large number of energy barriers but also have green and sustainable characteristics. In recent years, they have rapidly emerged in synthetic chemistry and biochemistry and have become a powerful experimental tool. Summary of the invention

[0007] The purpose of the present invention is to provide a safe, green and efficient method for preparing a polysubstituted five-membered heterocyclic compound. In order to achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0008] The first aspect of the present invention provides a method for preparing a polysubstituted five-membered heterocyclic compound, comprising the following steps:

[0009]

[0010] Wherein, in Formula III,

[0011] R1 is selected from C1 to C30 alkyl, R2 is selected from hydrogen, CN, C1-C30 alkyl, R3 is selected from hydrogen, CN, C1-C30 alkyl, R4 is selected from hydrogen, CN, C1-C30 alkyl, R5 is selected from hydrogen, CN, C1-C30 alkyl, R6 is selected from hydrogen, CN, C1-C30 alkyl, R7 is selected from hydrogen, C1-C30 alkyl;

[0012] R8 is selected from hydrogen, C1-C30 alkyl;

[0013] R9 is selected from hydrogen, C1-C30 alkyl;

[0014] R 10 Selected from hydrogen, C1-C30 alkyl;

[0015] R 11 Selected from hydrogen, C1-C30 alkyl;

[0016] R 12 Selected from hydrogen, C1-C30 alkyl;

[0017] R 13 Selected from hydrogen, C1-C30 alkyl, -CF3, -CHF2, R 14 Selected from hydrogen, C1-C30 alkyl, -CF3, -CHF2, R 15 Selected from hydrogen, C1-C30 alkyl, -CF3, -CHF2, R 16 is selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen (fluorine, chlorine, bromine, iodine); R 17 is selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen (fluorine, chlorine, bromine, iodine); R 18 is selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen (fluorine, chlorine, bromine, iodine); R 19is selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen (fluorine, chlorine, bromine, iodine); R 20 is selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen (fluorine, chlorine, bromine, iodine); in Formula II,

[0018] X is selected from S, O, -NR 23 ;

[0019] Y is selected from N, C;

[0020] R 21 Selected from CN, Z is selected from S, O, and N;

[0021] R 22 Selected from CN, R 23 Selected from R 24 Selected from hydrogen, C1-C30 alkyl;

[0022] R 25 Selected from hydrogen, C1-C30 alkyl;

[0023] Under argon conditions, a photocatalyst, a base, a compound II and a compound III in a molar ratio of 0.01 to 0.1:1 to 2:1:1 to 2 (preferably 0.01:1.5:1:1.3, 0.04:1.5:1:1.3) are mixed, a solvent is added, and after sealing, the mixture is illuminated under a light source with a photocatalyst excitation wavelength of 390 to 456 nm (preferably 456 nm), the light source is 5 to 8 cm (preferably 6 cm) away from the reaction bottle, the temperature is controlled to be 20 to 30° C. (preferably 25° C.), and the irradiation is continued for 1 to 5 hours (preferably 3 hours) to obtain the polysubstituted five-membered heterocyclic compound;

[0024] The photocatalyst is selected from 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine N1,N1′]bis[3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridyl N]phenyl-C]iridium(III) hexafluorophosphate, fac-Ir(2-phenylpyridyl)3, 3,4,5,6-tetrakis(9-carbazolyl)-o-phthalonitrile, 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile, 2,3,5,6-tetrakis(9-carbazolyl)-terephthalonitrile;

[0025] The base is selected from sodium carbonate, potassium carbonate, dipotassium hydrogen phosphate, potassium phosphate;

[0026] The solvent is selected from dichloromethane, acetonitrile, ethyl acetate, toluene, tetrahydrofuran, and 1,2-dichloroethane.

[0027] Preferably, in the compound represented by formula II,

[0028] X is selected from S, O, -NR 23 ;

[0029] Y is selected from N, C;

[0030]

[0031] Z is selected from S, O, and N;

[0032] R 22 Selected from CN,

[0033] R 23 Selected from

[0034] R 24 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl;

[0035] R 25 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl.

[0036] Most preferably, the compound represented by formula II is selected from one of the following structures:

[0037]

[0038] Preferably, in the compound represented by formula III,

[0039] R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,

[0040]

[0041] Most preferably, the compound represented by formula III is selected from one of the following structures:

[0042]

[0043] Preferably, the polysubstituted five-membered heterocyclic compound is selected from one of the following structures:

[0044]

[0045]

[0046] Due to the adoption of the above technical solution, the present invention has the following advantages and beneficial effects:

[0047] The present invention utilizes a photocatalytic dearomatization cycloaddition reaction under normal pressure to synthesize a polysubstituted five-membered heterocyclic compound, and has the advantages of simple synthesis process, mild conditions, easy operation, significantly improved synthesis yield, low environmental pollution, green environmental protection, etc., and the product has broad application prospects and market demand.

[0048] The present invention utilizes a photocatalytic free radical form 3+2 reaction at room temperature and pressure, and can be used for the later derivatization of five-membered heteroaromatic rings and sulfonamide drugs. It has the advantages of simple synthesis process, easy operation, significantly improved synthesis yield, low environmental pollution, and green environmental protection. DETAILED DESCRIPTION

[0049] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the content described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0050] Condition optimization experiment

[0051] 1. Photocatalyst screening, the reaction formula is as follows:

[0052]

[0053] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. A photocatalyst (as shown in Table 1), potassium phosphate (0.15 mmol, 31.8 mg), 3-methyl-1H-indole-1,3-dicarboxylic acid-1-tert-butyl ester (0.10 mmol, 27.5 mg) and N-cyclopropyl-4-methylbenzenesulfonamide (0.13 mmol, 27.4 mg) were added in sequence, and 1 mL of dichloromethane was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with an excitation wavelength of 456 nm for the photocatalyst (40 W Kessil lamp 390-456 nm), and the light source was about 6 cm away from the reaction bottle. The fan was used to cool the reaction bottle and the temperature was controlled at 25 ° C. After continuous irradiation for 3 hours, 5 mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50: 1) to obtain a polysubstituted five-membered heterocyclic compound.

[0054] The screening results are shown in Table 1:

[0055] Table 1

[0056]

[0057] In Table 1, various photocatalysts are used to catalyze the above reaction. The yield of 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile is better, reaching 48%. The yield of 3,4,5,6-tetrakis(9-carbazolyl)-ophthalonitrile is the second best, reaching 43%.

[0058] 2. Screening of base, the reaction formula is as follows:

[0059]

[0060] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile (0.004mmol, 3.2mg), base, 3-methyl-1H-indole-1,3-dicarboxylic acid-1-tert-butyl ester (0.10mmol, 27.5mg) and N-cyclopropyl-4-methylbenzenesulfonamide (0.13mmol, 27.4mg) were added in sequence, and 1mL of dichloromethane was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with a wavelength of 456nm for photocatalyst excitation (40Wkessil lamp 390-456nm), and the light source was about 6cm away from the reaction bottle. The fan was used to cool the reaction bottle and the temperature was controlled at 25°C. After continuous irradiation for 3 hours, 5mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50:1) to obtain a polysubstituted five-membered heterocyclic compound.

[0061] The screening results are shown in Table 2:

[0062] Table 2

[0063] Alkali Dosage Yield % Sodium carbonate 0.15mmol, 15.9mg, 1.5eq. 25 Potassium carbonate 0.15mmol, 20.7mg, 1.5eq. 40 Dipotassium hydrogen phosphate 0.15mmol, 26.1mg, 1.5eq. 29 Potassium bicarbonate 0.15mmol, 15mg, 1.5eq. trace Potassium Phosphate 0.15mmol, 31.8mg, 1.5eq. 48 Sodium acetate 0.15mmol, 12.3mg, 1.5eq. Trace

[0064] As can be seen from the data in Table 2, the yield of potassium phosphate is good, with a yield of 48%.

[0065] 3. Solvent screening, the reaction formula is as follows:

[0066]

[0067] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile (0.004mmol, 3.2mg), potassium phosphate (0.15mmol, 31.8mg), 3-methyl-1H-indole-1,3-dicarboxylic acid-1-tert-butyl ester (0.10mmol, 27.5mg) and N-cyclopropyl-4-methylbenzenesulfonamide (0.13mmol, 27.4mg) were added in sequence, and 1mL of solvent was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with a wavelength of 456nm for photocatalyst excitation (40Wkessil lamp 390-456nm), and the light source was about 6cm away from the reaction bottle. The fan was used to cool the reaction bottle and the temperature was controlled at 25°C. After continuous irradiation for 3 hours, 5mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50:1) to obtain a polysubstituted five-membered heterocyclic compound.

[0068] The screening results are shown in Table 3:

[0069] Table 3

[0070] Solvents Yield % Dichloromethane 48 Acetonitrile 8 N,N-Dimethylformamide trace Ethyl acetate 21 Toluene 32 Tetrahydrofuran 21 1,2-Dichloroethane 85

[0071] From the data in Table 3, it can be seen that the yield is best (85%) when the solvent is 1,2-dichloroethane.

[0072] Example 1

[0073]

[0074] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile (0.004mmol, 3.2mg), potassium phosphate (0.15mmol, 31.8mg), compound II-1 (0.10mmol, 27.5mg) and compound III-1 (0.13mmol, 27.4mg) were added in sequence, and 1mL of 1,2-dichloroethane was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with a wavelength of 456nm for photocatalyst excitation (40Wkessil lamp 390-456nm), and the light source was about 6cm away from the reaction bottle. The fan was used to cool the reaction bottle and the temperature was controlled at 25°C. After continuous irradiation for 3 hours, 5mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50:1) to obtain 41.3mg of a polysubstituted five-membered heterocyclic compound. The diastereoselectivity percentage of compound 1a and compound 1b was 48%:52%. (1a): 1 H NMR (500MHz, CDCl3): δ=7.83–7.81(m,1H),7.75–7.73(m,1H),7.30(d,J=7.9 Hz,2H),7.22(t,J=7.8Hz,1H),6.93(t,J=7.5Hz,1H),5.32(s,1H),4.98(d,J= 32.2Hz,1H),3.93(dt,J=10.3,5.6Hz,1H),3.66(s,3H),2.43(s,3H),2.31(d ,J=13.7Hz,1H), δ1.75(m,J=6.7,4.4Hz,1H),1.68–1.58(m,1H),1.52(s,9H). 13 C NMR (125MHz,CDCl3):δ= 13 C NMR (126MHz, CDCl3) δ173.0,151.5,144.8,143.7,137.7,129.8,129.7,128.0,127.2,124 .8,122.5,114.7,81.5,68.3,62.5,61.8,53.0,31.4,31.3,28.5,21.7.HRMS(ESI):calcd for(M+H)+ C 25 H 30 N2O6S requires m / z 487.1897, found m / z 487.1899. (1b): 1 1H NMR (500 MHz, CDCl3): δ = 7.89 (s, 1H), 7.81–7.69 (m, 2H), 7.44 (d, J = 7.6 Hz, 1H), 7.31 (d, J = 8.1 Hz, 3H), 7.27 (t, J = 8.0 Hz, 1H), 7.05–6.97 (m, 1H), 5.06–4.82 (m, 1H), 4.44 (dd, J = 10.0, 3.3 Hz, 1H), 4.23 (dt, J = 10.5, 5.4 Hz, 1H), 3.65 (s, 3H), 2.42 (s, 3H), 2.01 (s, 2H), 1.99–1.91 (m, 1H), 1.79–1.65 (m, 1H), 1.52 (s, 9H), 1.31–1.15 (m, 1H). 13 13C NMR (126 MHz, CDCl3). 13 13C NMR (125 MHz, CDCl3) δ 172.2, 143.8, 143.7, 139.3, 137.7, 129.9, 129.8, 129.5, 128.8, 127.2, 126.6, 125.6, 122.9, 114.8, 81.3, 67.1, 64.5, 53.1, 31.4, 28.5, 21.7. HRMS (ESI): (M + H) + calcd for C 25 H 30 N2O6S requires m / z 487.1897, found m / z 487.1890.

[0075] Example 2

[0076]

[0077] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile (0.004mmol, 3.2mg), potassium phosphate (0.15mmol, 31.8mg), compound II-1 (0.10mmol, 27.5mg) and compound III-2 (0.13mmol, 28.9mg) were added in sequence, and 1mL of 1,2-dichloroethane was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with a wavelength of 456nm for photocatalyst excitation (40Wkessil lamp 390-456nm), and the light source was about 6cm away from the reaction bottle. The fan was used to cool the reaction bottle and the temperature was controlled at 25°C. After continuous irradiation for 3 hours, 5mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50:1) to obtain 35.8mg of a polysubstituted five-membered heterocyclic compound. The diastereoselectivity percentage of compound 2a and compound 2b was 51%:49%. (2a) 1 H NMR (500MHz, CDCl3): δ=8.03–7.96(m,2H),7.90(s,1H),7.85–7.78(m,2H),7.36–7.26(m,2H),7.00(td,J=7.4,1.1Hz,1H),4.89(s,1H),4.65( d,J=9.8Hz,1H),4.30(td,J=10.7,5.6Hz,1H),3.66(s,3H),2.06(s,1H) ,2.02–1.90(m,1H),1.78–1.73(m,1H),1.54(s,9H),1.31–1.23(m,1H). 13 C NMR (125MHz, CDCl3): δ=172.8,151.6,145.0,133.5,133.0,129.9,127.8,127.5,122 .5,117.4,116.6,114.9,81.7,68.4,61.8,53.2,32.6,31.4,28.5.HRMS(ESI):(M+H) + Calculate for C 25 H 27 N3O6S requires m / z498.1693,found m / z 498.1690.(2b) 1H NMR (500MHz, CDCl3): δ=8.04–7.97(m,2H),7.86–7.82(m,2H),7.26(t,J=7.7Hz,1H),7.21(s,1H),6.93(t,J=7.5Hz,1H ),5.77(s,1H),4.96(s,1H),3.95(s,1H),3.69(s,3H),2.38(s,1H),1.84–1.78(m,1H),1.66–1.65(m,2H),1.56(s,9H). 13 C NMR (125MHz, CDCl3): δ=172.3,151.6,145.1,133.1,129.8,128.6,127.8,125.0,122 .9,117.4,116.6,115.0,81.6,67.1,64.6,53.2,32.3,31.6,28.5.HRMS(ESI):(M+H) + Calculate for C 25 H 27 N3O6Srequires m / z 498.1693,foundm / z 498.1700.

[0078] Example 3

[0079]

[0080] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile (0.004mmol, 3.2mg), potassium phosphate (0.15mmol, 31.8mg), compound II-1 (0.10mmol, 27.5mg) and compound III-3 (0.13mmol, 31.1mg) were added in sequence, and 1mL of 1,2-dichloroethane was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with a wavelength of 456nm for photocatalyst excitation (40Wkessil lamp 390-456nm), and the light source was about 6cm away from the reaction bottle. The fan was used to cool the reaction bottle and the temperature was controlled at 25°C. After continuous irradiation for 3 hours, 5mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50:1) to obtain 35.8mg of a polysubstituted five-membered heterocyclic compound. The diastereoselectivity percentage of compound 3a and compound 3b was 53%:47%. (3a) 1H NMR(500MHz,CDCl3):δ7.93(s,1H),7.54(d,J=7.6Hz,1H),7.31(t,J=7.7Hz,1H),7.13–7.05(m,1H),6.98(d,J=3.4Hz,3H),4.95(d,J=73.4Hz,1H),4.47(t,J=10.0Hz,1H),4.15(td,J=10.8,5.5Hz,1H),3.65(d,J=1.7Hz,3H),2.62(d,J=1.5Hz,6H),2.33(d,J=1.9Hz,3H),2.11–2.03(m,1H),2.03–1.92(m,1H),1.80(dt,J=12.1,5.8Hz,9H),1.55(s,3H),1.36–1.21(m,1H). 13 C NMR(125MHz,CDCl3):δ173.2,151.6,142.5,142.4,139.6,139.3,134.0,133.6,132.1,132.0,129.8,122.5,114.7,81.4,68.5,61.8,53.0,31.2,28.5,23.8,23.1,21.1,6.0.HRMS(ESI):(M+H) + calcdfor C 27 H 34 N2O6Srequires m / z 515.2210,found m / z 515.2215.(3b) 1 H NMR(500MHz,CDCl3):δ=7.81(d,J=8.2Hz,1H),7.39(s,1H),7.24-7.17(m,1H),7.15–7.00(m,2H),6.97(s,1H),6.86(t,J=7.5Hz,1H),5.28(d,J=9.4Hz,1H),4.95(d,J=36.9Hz,1H),3.84(d,J=8.7Hz,1H),3.65(s,3H),2.62(s,6H),2.35(d,J=5.9Hz,1H),2.31(s,3H),1.85–1.67(m,3H),1.53(s,9H). 13C NMR (125MHz, CDCl3):172.5,151.6,142.5,139.0,138.3,134.5,132.2,130.0,129.4,125.4,122.9 ,114.8,81.3,77.4,77.2,76.9,67.4,65.1,64.5,53.0,32.5,31.6,28.5,23.1,21.1.HRMS(ESI):C 27 H 34 N2O6S(M+H) + calcd for requires m / z515.2210, found m / z 515.2218.

[0081] Example 4

[0082]

[0083] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile (0.004mmol, 3.2mg), potassium phosphate (0.15mmol, 31.8mg), compound II-1 (0.10mmol, 27.5mg) and compound III-4 (0.13mmol, 21.2mg) were added in sequence, and 1mL of 1,2-dichloroethane was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with a wavelength of 456nm for photocatalyst excitation (40Wkessil lamp 390-456nm), and the light source was about 6cm away from the reaction bottle. The fan was used to cool the reaction bottle and the temperature was controlled at 25°C. After continuous irradiation for 3 hours, 5mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50:1) to obtain 39.9mg of a polysubstituted five-membered heterocyclic compound. The diastereoselectivity percentage of compound 4a and compound 4b was 46%:54%. (4a) 1 H NMR (500MHz, CDCl3): δ7.91 (d, J=3.1Hz, 1H), 7.44 (dd, J=7.7, 1.3Hz, 1H), 7.3 1–7.26(m,1H),7.01(td,J=7.5,1.1Hz,1H),4.94(s,1H),4.33(td,J=10.8,5.1 Hz,1H),4.11(d,J=10.5Hz,1H),3.74(s,3H),3.16–3.04(m,2H),2.17–1.95(m, 3H),1.88–1.79(m,2H),1.55(s,9H),1.44–1.29(m,1H),1.07(t,J=7.3Hz,3H); 1313C NMR (125 MHz, CDCl3): 173.1, 151.6, 129.9, 127.2, 122.5, 114.9, 68.2, 61.7, 55.6, 53.8, 53.1, 32.1, 28.5, 24.3, 17.6, 17.3, 13.1, 13.1, 6.6. HRMS (ESI): calcd for C 21 H 30 N2O6S (M+H) + requires m / z 439.1897, found m / z 439.1890. (4b) 1 1H NMR (500 MHz, CDCl3): δ 7.85 (s, 1H), 7.52 (d, J=7.6 Hz, 1H), 7.26 (d, J=1.7 Hz, 1H), 7.01 (td, J=7.5, 1.1 Hz, 1H), 5.04 (d, J=24.2 Hz, 2H), 4.09 (dt, J=10.1, 5.0 Hz, 1H), 3.75 (s, 3H), 3.00 (ddd, J=9.9, 6.3, 1.6 Hz, 2H), 2.39 (s, 1H), 1.94–1.78 (m, 6H), 1.57 (d, J=13.1 Hz, 10H), 1.07 (t, J=7.5 Hz, 3H). 13 13C NMR (125 MHz, CDCl3): δ 172.1, 151.6, 142.5, 129.7, 128.9, 125.5, 122.9, 114.9, 81.4, 66.9, 65.6, 64.6, 55.8, 53.1, 32.5, 32.4, 28.6, 17.5, 13.1. HRMS (ESI): calcd for C 21 H 30 N2O6S (M+H) + requires m / z 439.1897, found m / z 439.1895.

[0084] Example 5

[0085]

[0086] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile (0.004mmol, 3.2mg), potassium phosphate (0.15mmol, 31.8mg), compound II-2 (0.10mmol, 24.2mg) and compound III-1 (0.13mmol, 27.4mg) were added in sequence, and 1mL of 1,2-dichloroethane was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with a wavelength of 456nm for photocatalyst excitation (40Wkessil lamp 390-456nm), and the light source was about 6cm away from the reaction bottle. The fan was used to cool the temperature and control the temperature to 25°C. After continuous irradiation for 3 hours, 5mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50:1) to obtain 33.1mg of a polysubstituted five-membered heterocyclic compound. The diastereoselectivity percentage of compound 5a and compound 5b was 40%:60%. (5a) 1 H NMR (500MHz, CDCl3): δ7.87 (s, 1H), 7.83 (d, J = 8.1Hz, 2H), 7.35 (d, J = 8.0Hz, 2H),7.31(t,J=7.9Hz,1H),7.25(s,1H),7.02(t,J=7.5Hz,1H),4.95(s,1H),4 .42(d,J=10.2Hz,1H),4.25(td,J=11.0,5.8Hz,1H),2.45(s,3H),2.11(s,1H ),2.08–1.98(m,1H),1.84(dt,J=12.3,5.9Hz,1H),1.62(s,1H),1.54(s,9H); 13 C NMR(125MHz, CDCl3):144.3,137.2,130.1,127.3,126.8,123.3,120.5,115.2,82.4,69.4,63.2,49.2,31.4,30.6,28.5,21.8.HRMS(ESI):(M+H) + Calculate for C 24 H 27 N3O4S requires m / z454.1795,found m / z 454.1798.(5b) 1H NMR (500MHz, CDCl3): δ7.84(d,J=7.4Hz,1H),7.80(d,J=8.1Hz,2H),7.32(d,J=8.0Hz,2H),7.30–7.25(m,1H),7.11(s,1H ),6.93(t,J=7.5Hz,1H),5.61(s,1H),4.91(s,1H),3.82(q,J=7.9Hz,1H),2.44(s,3H),1.81–1.62(m,4H),1.53(s,9H).; 13 C NMR(125MHz, CDCl3):144.1,137.4,130.6,130.1,127.3,126.6,124.3,123.6, 119.0,115.4,82.1,68.8,64.2,53.5,32.5,31.4,28.5,21.7.HRMS(ESI):(M+H) + Calculate for C 24 H 27 N3O4S requires m / z 454.1795, found m / z 454.1781.

[0087] Example 6

[0088]

[0089] A magnetic stirrer was added to a dry reaction bottle, and argon was filled for protection. 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile (0.004mmol, 3.2mg), potassium phosphate (0.15mmol, 31.8mg), compound II-3 (0.10mmol, 19.2mg) and compound III-1 (0.13mmol, 27.4mg) were added in sequence, and 1mL of 1,2-dichloroethane was added to dissolve. After sealing, the reaction bottle was illuminated under a light source with a wavelength of 456nm for photocatalyst excitation (40Wkessil lamp 390-456nm), and the light source was about 6cm away from the reaction bottle. The fan was used to cool the temperature and control the temperature to 25°C. After continuous irradiation for 3 hours, 5mL of dichloromethane was added for dilution, and the reaction was concentrated under reduced pressure. The reaction was directly separated and purified by column chromatography (dichloromethane: methanol = 50:1) to obtain 25.8mg of a polysubstituted five-membered heterocyclic compound. The diastereoselectivity percentage of compound 6a and compound 6b was 47%:57%. (6a) 1H NMR(500MHz,CDCl3):δ7.73–7.68(m,2H),7.31(d,J=8.2Hz,2H),7.20(ddd,J=8.4,7.3,1.4Hz,1H),7.10(dd,J=7.9,1.1Hz,1H),7.06(dd,J=7.8,1.3Hz,1H),6.99(td,J=7.5,1.2Hz,1H),4.71(dd,J=7.0,2.2Hz,1H),4.42(td,J=9.6,5.8Hz,1H),4.23(d,J=9.8Hz,1H),3.66(s,3H),2.44(s,3H),2.19–2.05(m,1H),1.96–1.82(m,2H),1.81–1.65(m,1H); 13 C NMR(125MHz,CDCl3):171.7,159.8,143.8,137.7,130.0,129.9,127.2,126.1,125.7,121.0,109.7,89.60,77.4,77.2,76.9,68.1,64.4,53.0,32.2,31.2,21.7.HRMS(ESI):(M+H) + calcd for C 20 H 21 NO4S2 requires m / z404.0985,found m / z 404.0981.(6b) 1 H NMR(500MHz,CDCl3):δ7.75–7.67(m,1H),7.31–7.23(m,2H),7.17(td,J=7.6,1.3Hz,1H),7.09(dd,J=7.8,1.1Hz,0H),6.99(td,J=7.5,1.2Hz,1H),5.47(d,J=10.0Hz,1H),4.44(dd,J=8.1,6.2Hz,1H),4.17–4.00(m,1H),3.68(s,2H),2.42(s,2H),2.38–2.20(m,1H),1.82–1.69(m,1H),1.68–1.55(m,1H); 13 C NMR(125MHz,CDCl3):172.7,143.6,140.8,138.1,137.8,129.8,129.1,127.0,126.5,124.7,121.9,72.1,63.7,53.7,53.1,33.5,32.7,21.6.HRMS(ESI):(M+H) + calcd for C20 H 21 NO4S2requires m / z 404.0985,found m / z404.0979.

[0090] Example 7

[0091] According to the method and steps of Example 1, the structures of Compound II and Compound III are changed to obtain a multi-substituted five-membered heterocyclic compound. Some representative reaction results are shown in Table 4:

[0092] Table 4

[0093]

[0094]

[0095]

[0096]

[0097] 4ka, 4kb mixture, 40% yield. 1 H NMR (500MHz, CDCl3): δ8.76(s,1H),8.29(s,0H),7.88(d,J=5.7Hz,1H),7.78(d,J =8.2Hz,2H),7.54(s,1H),7.28(d,J=8.0Hz,2H),4.85(d,J=6.4Hz,1H),4.23(d,J =11.1Hz,1H),2.40(s,3H),2.34(s,3H),2.01(dd,J=14.4,6.2Hz,1H),1.85(tt,J =13.8,6.3Hz,1H),1.66(dt,J=12.3,6.1Hz,1H),1.53(s,9H),1.31–1.14(m,1H); 13 C NMR(125MHz, CDCl3):205.8,152.0,151.1,148.6,148.0,143.5,138.0,129.8,127.4,123.0 ,109.1,83.2,77.4,77.2,76.9,68.3,61.1,31.1,29.8,28.4,28.2,21.7.HRMS(ESI):calcd for C 24 H 29 N3O5S(M+H) + requires m / z 472.1901,foundm / z472.1905.

[0098]

[0099] 4o, 36% yield, 1 H NMR (500 MHz, CDCl3): δ 7.77–7.71 (m, 2H), 7.36–7.34 (m, 1H), 7.34–7.30 (m, 2H), 7.19–7.15 (m, 1H), 6.87 (td, J = 7.5, 1.0 Hz, 1H), 6.72 (dt, J = 8.1, 0.7 Hz, 1H), 5.47 (dd, J = 6.5, 2.5 Hz, 1H), 5.36 (d, J = 9.4 Hz, 1H), 4.01–3.98 (m, 1H), 3.70 (s, 3H), 2.43 (s, 1H), 2.21–2.14 (m, 1H), 1.96–1.91 (m, 1H), 1.69–1.54 (m, 2H); 13 C NMR (125 MHz, CDCl3): δ 171.7, 159.8, 143.8, 137.7, 130.0, 129.9, 127.2, 126.1, 125.7, 121.0, 109.7, 89.6, 77.4, 77.2, 76.9, 68.1, 64.3, 53.0, 32.2, 31.2, 21.7. HRMS (ESI): calcd for C 20 H 21 NO5S (M + H) + requires m / z 388.1213, found m / z 388.1215.

[0100]

[0101] 4pa, 4pb mixture, 48% yield. 1 H NMR (500 MHz, CDCl3): δ 7.77–7.69 (m, 2H), 7.32–7.28 (m, 2H), 6.37 (dd, J = 97.4, 2.7 Hz, 1H), 5.18–5.10 (m, 1H), 4.94 (d, J = 5.4 Hz, 1H), 4.92–4.88 (m, 1H), 4.83 (t, J = 8.0 Hz, 1H), 3.99–3.94 (m, 1H), 3.80–3.68 (m, 1H), 3.63 (d, J = 15.5 Hz, 3H), 2.42 (d, J = 1.6 Hz, 3H), 1.94–1.90 (m, 1H), 1.87–1.69 (m, 2H), 1.57–1.41 (m, 1H); 1313C NMR (125 MHz, CDCl3): δ 169.7, 147.8, 143.7, 137.6, 129.8, 127.2, 101.2, 100.1, 88.1, 86.7, 85.9, 84.1, 65.7, 63.5, 62.4, 52.6, 43.2, 41.3, 29.9, 29.2, 28.7, 21.7. HRMS (ESI): calcd for C 16 H 19 NO5S (M + H) + requires m / z 338.1057, found m / z 338.1059.

[0102]

[0103] 4qa, 4qb mixture, 52% yield. 1 1H NMR (500 MHz, CDCl3): δ 7.79–7.66 (m, 2H), 7.35–7.28 (m, 2H), 6.23 (dd, J = 102.7, 6.0 Hz, 1H), 5.40 (dd, J = 29.2, 6.0 Hz, 1H), 4.92 (dd, J = 184.1, 9.5 Hz, 1H), 4.49–4.23 (m, 1H), 4.14–3.70 (m, 1H), 3.66 (d, J = 17.9 Hz, 3H), 2.43 (s, 3H), 2.34–1.99 (m, 1H), 1.91–1.68 (m, 2H), 1.64–1.49 (m, 1H); 13 13C NMR (125 MHz, CDCl3): 174.4, 173.4, 143.7, 137.9, 137.5, 131.4, 129.9, 129.8, 127.5, 127.3, 127.1, 121.7, 118.4, 77.4, 77.2, 76.9, 74.2, 71.8, 63.2, 62.4, 54.0, 52.9, 52.8, 34.7, 33.3, 32.3, 31.6, 21.7. HRMS (ESI): calcd for C 16 H 19 NO4S2 (M + H) + requires m / z 354.0828, found m / z 354.0825.

[0104]

[0105] 5aa, 73% yield. 1H NMR(500MHz,CDCl3):δ7.99–7.81(m,3H),7.42–7.24(m,9H),6.98(td,J=7.5,1.1Hz,1H),4.89(s,1H),4.53(d,J=9.8Hz,1H),4.45–4.24(m,1H),3.65(s,3H),2.49(s,3H),2.06(s,1H),2.03-1.95(m,1H),1.80–1.72(m,1H),1.61–1.46(m,9H),1.40–1.21(m,1H); 13 C NMR(125MHz,CDCl3):δ172.9,167.3,161.2,151.6,139.9,135.4,130.4,129.8,128.8,128.6,127.8,127.6,122.5,114.8,114.6,109.7,81.6,77.4,77.2,76.9,68.4,62.1,61.8,60.0,58.2,56.3,53.1,31.4,28.5,11.9.HRMS(ESI):calcd forC 34 H 35 N3O7S(M+H) + requires m / z630.2269,found m / z 630.2256.

[0106] 5ab, 1 H NMR(500MHz,CDCl3):δ7.93–7.79(m,1H),7.48–7.15(m,11H),6.92(t,J=7.6Hz,1H),5.43(s,1H),4.96(s,1H),3.96(s,1H),3.66(s,3H),2.49(s,4H),2.35(d,J=1.7Hz,1H),1.82–1.75(m,1H),1.71–1.46(m,11H); 13 C NMR(125MHz,CDCl3):172.2,167.4,161.2,141.2,139.8,135.5,130.5,130.4,129.9,129.7,128.9,128.8,128.6,128.6,127.6,127.0,122.9,114.9,114.6,81.4,67.2,64.6,53.1,32.4,31.5,28.5,11.9.HRMS(ESI):calcd for C 34 H 35 N3O7S(M+H)+ requires m / z 630.2269,found m / z 630.2273.

[0107]

[0108] 5ba,68%yield。 1 H NMR(500MHz,CDCl3):δ7.90–7.82(m,3H),7.52–7.46(m,2H),7.36(d,J=7.6Hz,1H),7.29(td,J=7.9,1.3Hz,1H),7.16(d,J=8.0Hz,2H),7.12–7.09(m,2H),7.00(td,J=7.5,1.1Hz,1H),6.75(s,1H),4.88(s,1H),4.45(d,J=9.8Hz,1H),4.28(td,J=10.5,5.5Hz,1H),3.68(s,3H),2.37(s,3H),2.05(s,1H),2.00-1.92(m,1H),1.79–1.71(m,1H),1.54(s,9H),1.30–1.20(m,1H); 13 C NMR(125MHz,CDCl3):δ172.9,154.1,151.5,145.4,144.3(q,J C-F =38.5Hz),142.7,142.1,140.2,139.9,129.9,128.9,128.2,127.8,125.7,123.3(q,J C-F =268.6Hz),122.5,114.9,110.3,106.4,68.4,61.8,60.0,53.2,31.4,28.5,21.5.HRMS(ESI):calcd for C 35 H 35 F3N4O6S(M+H) + requires m / z697.2302,found m / z 697.2300.

[0109] 5bb, 1H NMR(500MHz,CDCl3):δ7.90–7.82(m,2H),7.51–7.45(m,2H),7.30(s,1H),7.15(d,J=8.0Hz,1H),7.09(d,J=8.1Hz,2H),7.01–6.93(m,2H),6.74(s,1H),5.58(d,J=36.0Hz,1H),5.00(d,J=46.6Hz,1H),3.95(dt,J=10.6,5.6Hz,1H),3.66(s,3H),2.36(s,3H),1.79–1.73(m,1H),1.69–1.44(m,11H); 13 C NMR(125MHz,CDCl3):172.2,151.6,145.4,144.22(d,J C-F =38.4Hz),142.7,140.2,139.9,129.9,129.7,128.8,128.7,128.1,125.8,125.7,123.0,121.2(d,J C-F =269.4Hz),114.9,106.4,81.4,67.1,65.3,64.6,53.1,32.4,31.4,28.5,21.4.HRMS(ESI):calcd for C 35 H 35 F3N4O6S(M+H) + requires m / z 697.2302,foundm / z 697.2311.

[0110]

[0111] 5da,74%yield。 1H NMR(500MHz,CDCl3):δ7.93–7.82(m,2H),7.53–7.43(m,2H),7.36(d,J=7.6Hz,1H),7.33–7.22(m,1H),6.99(dd,J=14.0,7.8Hz,2H),6.91(d,J=3.2Hz,2H),6.80–6.61(m,1H),4.87(s,1H),4.47(d,J=9.8Hz,1H),4.28(q,J=9.2Hz,1H),3.90–3.81(m,3H),3.68(d,J=1.9Hz,3H),2.05(s,1H),1.96(tt,J=13.6,6.3Hz,1H),1.80–1.65(m,1H),1.54(s,9H),1.31–1.17(m,1H); 13 C NMR(125MHz,CDCl3):δ172.9,152.2(d,J C-F =248.6Hz),148.7(d,J C-F =9.8Hz),148.5,148.2,143.8,142.7,140.0,129.9,128.3,125.5,125.3,122.5,121.7(d,J C-F =6.8Hz),116.7(d,J C-F =19.7Hz).,114.84,113.7,112.9,111.0,109.2,105.9,68.4,61.7,56.3,53.2,31.3,28.5.HRMS(ESI):calcdfor C 35 H 35 F3N4O7S(M+H) + requires m / z713.2251,found m / z 713.2243.

[0112] 5db, 11H NMR (500 MHz, CDCl3): δ 7.86 (d, J = 8.5 Hz, 1H), 7.46 (d, J = 8.5 Hz, 1H), 7.30 (s, 1H), 7.24 (t, J = 7.9 Hz, 1H), 6.98–6.93 (m, 1H), 6.91 (d, J = 4.2 Hz, 1H), 6.78–6.63 (m, 1H), 5.44 (t, J = 18.2 Hz, 1H), 4.98 (d, J = 48.2 Hz, 1H), 3.94 (dt, J = 10.3, 5.7 Hz, 1H), 3.89 (s, 2H), 3.67 (s, 2H), 2.41–2.25 (m, 1H), 1.83–1.71 (m, 1H), 1.69–1.49 (m, 6H); 13 13C NMR (125 MHz, CDCl3): 172.3, 152.2 (d, J C-F = 248.1 Hz), 148.7 (d, J C-F = 10.0 Hz), 148.5, 148.3, 143.8, 142.7, 140.1, 129.7, 128.2, 125.5, 125.3, 125.3, 123.0, 121.7 (d, J C-F = 7.1 Hz), 116.7 (d, J C-F = 19.7 Hz)., 114.9, 113.7, 112.9, 111.0, 109.2, 106.0, 81.42, 67.2, 65.2, 64.5, 56.3, 53.2, 32.4, 31.4, 28.5. HRMS (ESI): calcd for C 35 H 35 F3N4O7S (M + H) + requires m / z 713.2251, found m / z 713.2266.

[0113] Comparative Example 1

[0114] Vin-Cent Pirenne, Emma G.L. Robert, Jerome Waser. Catalytic [3+2] annulation of donor-acceptor aminocyclopropane monoesters and indoles. Chemical science, 2021, 12(25): 8706-8712.

[0115]

[0116] In a dry reaction bottle, first add dichloromethane (1 mL), then add bis(trifluoromethanesulfonyl)imide (0.2 M, 39 μL, 7.8 μmol, 2.5 mol%) and silyl acetal (16.8 mg, 77.8 μmol, 0.25 equiv) into the reaction bottle, dilute with 0.1 mL of anhydrous DCM, stir at room temperature for 10 minutes and then cool to -78 °C. Subsequently, (1R, 2R)-2-((N, 4-dimethyl) sulfonamide) cyclopropane-1-carboxylic acid ethyl ester (92.6 mg, 311 μmol, 1.0 eq.) and nitrogen methyl indole ((42 μL, 0.33 mmol, 1.05 eq.) were added and reacted with the preformed catalyst at -78°C for half an hour. 10 microliters of triethylamine were added to quench the reaction. After rotary evaporation and concentration, the mixture was extracted with dichloromethane and water three times (3*50 mL), the organic phase was dried over anhydrous sodium sulfate, and the organic layer was concentrated in vacuo. The crude reaction product was purified by silica gel column chromatography, and the product (127 mg, 296 μmol, 95%) was obtained by gradient elution with PE / EA=80 / 20, with a diastereoselectivity of 93:7.

[0117] Comparative Example 2

[0118] Hai-Xia Wang,Chun Yang,Hai-Ming Guo.et al.Design of C1-symmetrictridentate ligands for enantioselective dearomative[3+2]annulation of indoleswith aminocyclopropanes[J].Nature Communications,2023,14,2270.

[0119]

[0120] In a nitrogen-filled dry sealed tube, Ni(OTf)2 (3.6 mg, 0.01 mmol, 5 mol%), ligand L (7.9 mg, 0.012 mmol, 6 mol%) and 2-(2,5-dioxopyrrolidin-1-yl)cyclopropane-1,1-dicarboxylic acid dimethyl ester (112.2 mg, 0.44 mmol, 0.2 eq.) were added, and stirred at room temperature for 30 minutes under nitrogen atmosphere in DCM (3.0 mL) solvent. Then 1,3-dimethylindole (29.0 mg, 0.2 mmol, 1.0 eq.) was dissolved in DCM (1.0 mL) and added to the catalyst mixture via a syringe. The reaction was complete after 24 hours (TLC monitoring). After rotary evaporation and concentration, the mixture was extracted with dichloromethane and water 3 times (3*50 mL), the organic phase was dried over anhydrous sodium sulfate, and the organic layer was concentrated in vacuo. The crude product was purified by silica gel column chromatography (petroleum ether / ethyl acetate, v / v, 10:1-2:1) to obtain the product in a 72% yield as a white solid (90.1 mg).

[0121] Compared with comparative examples 1 and 2, the present invention has mild conditions, does not require the use of metals and strong acids, has a simple and green synthesis process, is easy to operate, has almost no by-products, has high atom economy, has little environmental pollution, is green and environmentally friendly, and is widely applicable to the post-modification of electron-deficient five-membered heteroaromatic rings and sulfonamide drugs. The present invention can ensure that the quality of the entire product is further improved, and has broad application prospects and market demand.

[0122] The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment, it is not used to limit the present invention. Any technician familiar with this patent can make some changes or modify the technical contents suggested above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the solution of the present invention.

Claims

1. A method for preparing a polysubstituted five-membered heterocyclic compound, characterized in that: The following steps are involved: Wherein, in Formula III, R1 is selected from C1 to C30 alkyl, R2 is selected from hydrogen, CN, C1-C30 alkyl, R3 is selected from hydrogen, CN, C1-C30 alkyl, R4 is selected from hydrogen, CN, C1-C30 alkyl, R5 is selected from hydrogen, CN, C1-C30 alkyl, R6 is selected from hydrogen, CN, C1-C30 alkyl, R7 is selected from hydrogen, C1-C30 alkyl; R8 is selected from hydrogen, C1-C30 alkyl; R9 is selected from hydrogen, C1-C30 alkyl; R 10 Selected from hydrogen, C1-C30 alkyl; R 11 Selected from hydrogen, C1-C30 alkyl; R 12 Selected from hydrogen, C1-C30 alkyl; R 13 Selected from hydrogen, C1-C30 alkyl, -CF3, -CHF2, R 14 Selected from hydrogen, C1-C30 alkyl, -CF3, -CHF2, R 15 Selected from hydrogen, C1-C30 alkyl, -CF3, -CHF2, R 16 Selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen; R 17 Selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen; R 18 Selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen; R 19 Selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen; R 20 Selected from hydrogen, C1-C30 alkyl, C1-C30 alkoxy, halogen; In formula II, X is selected from S, O, -NR 23 ; Y is selected from N, C; R 21 Selected from CN, Z is selected from S, O, and N; R 22 Selected from CN, R 23 Selected from R 24 Selected from hydrogen, C1-C30 alkyl; R 25 Selected from hydrogen, C1-C30 alkyl; Under argon conditions, a photocatalyst, a base, a compound II and a compound III in a molar ratio of 0.01 to 0.1:1 to 2:1:1 to 2 are mixed, a solvent is added, and after sealing, the mixture is illuminated under a light source with a photocatalyst excitation wavelength of 390 to 456 nm, the light source is 5 to 8 cm away from the reaction bottle, the temperature is controlled at 20 to 30° C., and the irradiation is continued for 1 to 5 hours to obtain the polysubstituted five-membered heterocyclic compound; The photocatalyst is selected from 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine N1,N1′]bis[3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridyl N]phenyl-C]iridium(III) hexafluorophosphate, fac-Ir(2-phenylpyridyl)3, 3,4,5,6-tetrakis(9-carbazolyl)-o-phthalonitrile, 2,4,5,6-tetrakis(diphenylamino)-isophthalonitrile, 2,3,5,6-tetrakis(9-carbazolyl)-terephthalonitrile; The base is selected from sodium carbonate, potassium carbonate, dipotassium hydrogen phosphate, potassium phosphate; The solvent is selected from dichloromethane, acetonitrile, ethyl acetate, toluene, tetrahydrofuran, and 1,2-dichloroethane.

2. The method for preparing a polysubstituted five-membered heterocyclic compound according to claim 1, characterized in that: In the compound represented by formula II, X is selected from S, O, -NR 23 ; Y is selected from N, C; R 21 Selected from CN, Z is selected from S, O, and N; R 22 Selected from CN, R 23 Selected from R 24 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl; R 25 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl.

3. The method for preparing a polysubstituted five-membered heterocyclic compound according to claim 2, characterized in that: The compound represented by formula II is selected from one of the following structures:

4. The method for preparing a polysubstituted five-membered heterocyclic compound according to claim 1, characterized in that: In the compound represented by formula III, R1 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 5. The method for preparing a polysubstituted five-membered heterocyclic compound according to claim 4, characterized in that: The compound represented by formula III is selected from one of the following structures:

6. The method for preparing a polysubstituted five-membered heterocyclic compound according to claim 1, characterized in that: The polysubstituted five-membered heterocyclic compound is selected from one of the following structures:

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