An organic photocatalytic synthesis method of a phenanthridine heterocyclic carbonyl compound

Abstract

The present invention provides an organic photocatalytic synthesis method of a phenanthridine heterocyclic carbonyl compound. The organic photocatalyst is a nitrene, belonging to the technical field of organic synthesis. The organic photocatalyst and the compounds shown in Formula II and Formula III are dissolved in a solvent to obtain a reaction solution to be reacted; the obtained reaction solution to be reacted is subjected to an addition reaction under blue light to obtain the phenanthridine heterocyclic carbonyl compound. The organic photocatalyst provided by the present invention is economical and green. Compared with the prior art, the organic photocatalytic synthesis method described in the present invention has the characteristics of easily available raw materials, metal-free catalysis, economical and green reaction conditions, etc.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to an organic photocatalytic synthesis method of a phenanthridine heterocyclic carbonyl compound. Background Art

[0002] Compared with acyl chlorides, acyl fluorides have become precursors for many reactions due to their greater stability and easy availability (Angew. Chem. Int. Ed. 2019, 58, 6814 - 6817; Angew. Chem. Int. Ed. 2020, 59, 574–594), including fluorination reactions, deacylative couplings, and acyl couplings, etc. (J. Fluorine Chem. 2021, 248, 109806; Synthesis 2022, 54, 3667 - 3697; Nature 2018, 563, 100 - 104; Angew. Chem. Int. Ed. 2018, 57, 4073 - 4077; Chem. Eur. J. 2019, 25, 9410 - 9414; Org. Lett. 2020, 22, 6388 - 6393; Organometallics 2020, 39, 856 - 861; J. Am. Chem. Soc. 2022, 144, 7072 - 7079). However, the reaction using it as an acyl radical precursor has not been established. In recent years, the research on photocatalytic generation of acyl radicals under mild conditions has been increasing day by day. However, most of these photocatalytic methods require expensive metal photocatalysts or other additives (Green Chem. 2019, 21, 748 - 764; Synthesis 2019, 51, 303 - 333; Nat Catal. 2020, 3, 872 - 886). In this regard, developing inexpensive organic photocatalysts and applying them to acyl chemistry is a direction worthy of exploration.

[0003] Heterocyclic compounds, as the main skeletons in drug and pesticide development, are common in natural products and bioactive-related compounds. Among them, phenanthridine and its derivatives have been proven to have significant biological and cellular effects and can be used as potential drug candidates (J. Nat. Prod. 2004, 67, 1119 - 1124; J. Med. Chem. 2008, 51, 6699 - 6710; J. Am. Chem. Soc. 2008, 130, 7182 - 7183; J. Am. Chem. Soc. 2014, 136, 2583 - 2591; Bioorg. Med. Chem. Lett. 2014, 24, 2712 - 2716). To obtain phenanthridine carbonyl derivatives, cascade reactions of many acyl radical precursors and 2-isocyanobiphenyl have been developed, and most of these strategies require the participation of strong oxidants and transition metals (Org. Lett. 2013, 15, 6286 - 6289; Chem. Commun. 2014, 50, 2145 - 2147; Green Chem. 2021, 23, 6926 - 6930; Green Chem. 2014, 16, 2418 - 2421; Tetrahedron 2016, 72, 8350 - 8357).

[0004] Currently, green chemistry is the main goal in the development of new reactions. Therefore, it is of great value to develop new stable radical precursors and new catalytic systems to introduce carbonyl structural units into organic molecules economically and greenly. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide an organic photocatalytic synthesis method for phenanthridine heterocyclic carbonyl compounds.

[0006] To achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0007] The present invention also provides an organic photocatalytic synthesis method for phenanthridine heterocyclic carbonyl compounds, including the following steps:

[0008] 1) Dissolve an organic photocatalyst and the compounds shown in Formula II and Formula III in a solvent to obtain a reaction solution to be reacted;

[0009] The organic photocatalyst has the structural formula shown in Formula I:

[0010]

[0011] 2) Carry out an addition reaction on the reaction solution to be reacted obtained in step 1) under blue light to obtain a phenanthridine heterocyclic carbonyl compound;

[0012] The structural formulas of Formula II and Formula III are:

[0013]

[0014] In formula II, Ar is an aromatic ring;

[0015] In formula III, R 1 is any one of mono-substituted or multi-substituted alkyl, halogen, and methoxy, and R 2 is any one of mono-substituted or multi-substituted alkyl, halogen, and methoxy.

[0016] Preferably, the structural formula of the phenanthridine heterocyclic carbonyl compound is as shown in formula IV:

[0017]

[0018] Among them, R 1 is any one of mono-substituted or multi-substituted alkyl, halogen, and methoxy, and R 2 is any one of mono-substituted or multi-substituted alkyl, halogen, and methoxy.

[0019] Preferably, the compound shown in IV is any one of the compounds shown in formula IV-1 to formula IV-20 below:

[0020]

[0021] Preferably, the compound shown in formula II is any one of the compounds shown in formula II-1 to formula II-9 below:

[0022]

[0023] Preferably, the compound shown in formula III is any one of the compounds shown in formula III-1 to III-12 below:

[0024]

[0025] Preferably, in step 1), the molar ratio of the organic photocatalyst to the compounds shown in formula II and formula III is 0.03:0.3:0.15.

[0026] Preferably, the solvent in step 1) includes acetonitrile, and the concentration of the compound shown in formula III in the reaction solution to be reacted is 0.1 mol / L.

[0027] Preferably, the wavelength of the blue light in step 2) is 450 nm.

[0028] Preferably, the conditions for the addition reaction in step 2) include: the temperature is 40-50 °C and the time is 12 h.

[0029] The beneficial effects of the present invention are:

[0030] Compared with the prior art, the synthesis method of the heterocyclic derivative of the present invention has the characteristics of easy availability of raw materials, metal-free catalysis, economical and green reaction conditions, etc. Description of the Drawings

[0031] Figure 1 It is a synthetic route diagram of the phenanthridine heterocyclic carbonyl compound in a specific embodiment of the present invention. Detailed Embodiments

[0032] The present invention provides an organic photocatalytic synthesis method of a phenanthridine heterocyclic carbonyl compound, comprising the following steps:

[0033] 1) Dissolve the organic photocatalyst and the compounds shown in Formula II and Formula III in a solvent to obtain a reaction solution to be reacted;

[0034] The organic photocatalyst has the structural formula shown in Formula I:

[0035]

[0036] 2) Carry out an addition reaction on the reaction solution to be reacted obtained in the step 1) under blue light to obtain a phenanthridine heterocyclic carbonyl compound;

[0037] The structural formulas of Formula II and Formula III are:

[0038]

[0039] In Formula II, Ar is an aromatic ring;

[0040] In Formula III, it is R 1 is any one of a mono-substituted or multi-substituted alkyl group, a halogen, and a methoxy group, R 2 is any one of a mono-substituted or multi-substituted alkyl group, a halogen, and a methoxy group.

[0041] The present invention dissolves the organic photocatalyst and the compounds shown in Formula II and Formula III in a solvent to obtain a reaction solution to be reacted.

[0042] The present invention has no special limitation on the source of the organic photocatalyst, and it can be obtained by using a conventional commercially available product or a preparation method. In the specific embodiment of the present invention, the organic photocatalyst is preferably prepared according to the literature of Boche, G., Andrews, P., Harms, K., Marsch, M., Rangappa, K. S., Schimeczek, M., Willeke, C. J. Am. Chem. Soc. 1996, 118, 4925-4930.

[0043] In the present invention, the molar ratio of the organic photocatalyst to the compounds represented by Formula II and Formula III is preferably 0.03:0.3:0.15. In the present invention, the solvent preferably includes acetonitrile, and the concentration of the compound represented by Formula III in the reaction solution to be reacted is preferably 0.1 mol / L.

[0044] In the present invention, the structural formula of the phenanthridine heterocyclic carbonyl compound is preferably as shown in Formula IV:

[0045]

[0046] Wherein, R 1 is any one of a mono-substituted or multi-substituted alkyl group, a halogen, and a methoxy group, and R 2 is any one of a mono-substituted or multi-substituted alkyl group, a halogen, and a methoxy group.

[0047] In the present invention, the compound represented by Formula IV is preferably any one of the compounds represented by Formula IV-1 to Formula IV-20 below:

[0048]

[0049] In the present invention, the compound represented by Formula II is preferably any one of the compounds represented by Formula II-1 to Formula II-9 below:

[0050]

[0051] In the present invention, the compound represented by Formula III is preferably any one of the compounds represented by Formula III-1 to Formula III-12 below:

[0052]

[0053] In the present invention, the synthesis reaction is preferably carried out in an inert atmosphere. In the present invention, the wavelength of the blue light is preferably 450 nm, the blue light is preferably provided by a blue LED lamp, and the power of the LED lamp is preferably 38 W. In the present invention, the conditions for the addition reaction preferably include: the temperature is 40-50 °C, and the time is 12 h.

[0054] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0055] The experimental methods used in the following embodiments are all conventional methods unless otherwise specified. 1 1H NMR and 13 13C NMR were measured by a Bruker nuclear magnetic resonance spectrometer. The materials, reagents, etc. used in the following embodiments can be obtained from commercial sources unless otherwise specified.

[0056] Example 1

[0057] Synthesize the compound shown in Formula IV-1

[0058] According to Figure 1 the synthetic route diagram shown, synthesize the compound shown in Formula IV-1. The specific steps are as follows:

[0059] Add the pre-dried 10 mL reaction tube under nitrogen protection with the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). Stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp at 45 °C. Then perform vacuum distillation on the reaction mixture. After concentration, perform silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1. After collection, perform vacuum distillation to obtain the product), so as to obtain the compound shown in Formula IV-1.

[0060]

[0061] The experimental data for structure verification are as follows:

[0062] A white solid (30.6 mg, 0.108 mmol, yield 72%). 1 H NMR (500 MHz, Chloroform-d): δ 8.63 (d, J = 8.4 Hz, 1H), 8.56 (dd, J = 7.6, 2.1 Hz, 1H), 8.14–8.12 (m, 1H), 8.06 (d, J = 8.2 Hz, 1H), 7.96 (dd, J = 8.2, 1.4 Hz, 2H), 7.79–7.82 (m, 1H), 7.74–7.63 (m, 2H), 7.62–7.49 (m, 2H), 7.38–7.41 (m, 2H). 13 C NMR (126 MHz, Chloroform-d): δ 195.0, 157.6, 142.8, 136.3, 134.1, 133.4, 131.4, 131.0, 130.8, 129.2, 128.7, 128.3, 127.9, 127.5, 124.6, 123.9, 122.5, 122.3 (IV-1 is consistent with the reported structure in the literature. The literature is as follows, Leifert, D.; Daniliuc, C.G.; Studer, A. Org. Lett. 2013, 15, 6286–6289).

[0063] After verification, the obtained compound is the compound shown in Formula IV-1.

[0064] Example 2

[0065] Synthesize the compound shown in Formula IV-2

[0066] According to Figure 1 The synthetic route diagram shown, synthesize the compound shown in Formula IV-2. The specific steps are as follows:

[0067] Add the pre-dried 10 mL reaction tube under nitrogen protection with the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-2 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). Stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp at 45 °C. Then perform vacuum distillation on the reaction mixture. After concentration, perform silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1. After collection, perform vacuum distillation to obtain the product), so as to obtain the compound shown in Formula IV-2.

[0068]

[0069] The experimental data for structure verification are as follows:

[0070] A white solid (28.5 mg, 0.096 mmol, yield 64%). 1 H NMR (500 MHz, Chloroform-d): δ 8.62–8.58 (m, 2H), 8.20–8.16 (m, 1H), 8.05–8.01 (m, 2H), 7.90 (s, 1H), 7.76–7.71 (m, 3H), 7.64–7.60 (m, 1H), 7.50–7.46 (m, 2H), 2.51 (s, 3H). 13 C NMR (126 MHz, Chloroform-d): δ 195.1, 157.4, 142.5, 138.1, 136.3, 134.1, 133.3, 131.4, 131.0, 130.7, 128.8, 128.7, 128.3, 126.7, 124.7, 124.1, 122.4, 122.1, 21.8 (IV-2 is consistent with the reported structure in the literature. The literature is as follows, Leifert, D.; Daniliuc, C.G.; Studer, A. Org. Lett. 2013, 15, 6286–6289).

[0071] After verification, the obtained compound is the compound shown in Formula IV-2.

[0072] Example 3

[0073] Compound shown in Formula IV-3

[0074] According to Figure 1 the synthetic route diagram shown, the compound shown in Formula IV-3 is synthesized. The specific steps are as follows:

[0075] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-3 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), acetonitrile (1.5 mL). Under the condition of 45 °C, stir overnight (12 h) under the irradiation of a 38 W blue LED (450 nm) lamp. Then carry out vacuum distillation on the reaction mixture, and after concentration, carry out silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1, and the product is obtained after collection and vacuum distillation) to obtain the compound shown in Formula IV-3.

[0076]

[0077] The experimental data for structure verification are as follows:

[0078] A white solid (20.8 mg, 0.062 mmol, yield 41%). Melting point: 150–151 °C. 1 1H NMR (500 MHz, Chloroform-d): δ 8.67–8.60 (m, 2H), 8.21–8.17 (m, 1H), 8.10 (d, J = 2.0 Hz, 1H), 8.04 (dd, J = 8.2, 1.4 Hz, 2H), 7.98 (dd, J = 8.8, 2.0 Hz, 1H), 7.76–7.72 (m, 2H), 7.60–7.64 (m, 1H), 7.50–7.46 (m, 2H), 1.37 (s, 9H). 13 13C NMR (126 MHz, Chloroform-d): δ 195.2, 157.5, 151.1, 142.6, 136.5, 134.0, 131.4, 131.0, 130.7, 129.9, 128.8, 128.7, 128.3, 124.7, 124.0, 122.9, 122.3, 122.2, 35.2, 31.3. IR (ATR): 2980, 2903, 2167, 2028, 1407, 1252, 1054 cm -1 . HRMS (ESI) m / z: [M+Na] + calcd. for C 24 H 21 NONa +363.1515, found 363.1515。

[0079] It was verified that the obtained compound was the compound shown in Formula IV-3.

[0080] Example 4

[0081] Synthesize the compound shown in Formula IV-4

[0082] According to Figure 1 the synthetic route map shown, synthesize the compound shown in Formula IV-4. The specific steps are as follows:

[0083] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-4 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), acetonitrile (1.5 mL). Under the condition of 45 °C, stir overnight (12 h) under the irradiation of a 38 W blue LED (450 nm) lamp. Then carry out vacuum distillation on the reaction mixture. After concentration, carry out silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 20:1. After collection, carry out vacuum distillation to obtain the product), so as to obtain the compound shown in Formula IV-4.

[0084]

[0085] The experimental data for structure verification are as follows:

[0086] A white solid (21.1 mg, 0.068 mmol, the yield was 45%). 1 H NMR (500 MHz, Chloroform-d): δ 8.65–8.60 (m, 1H), 8.59–8.55 (m, 1H), 8.21–8.15 (m, 1H), 8.05 (dd, J = 8.3, 1.4 Hz, 2H), 7.70–7.76 (m, 2H), 7.67–7.60 (m, 1H), 7.56–7.45 (m, 4H), 3.88 (s, 3H). 13 C NMR (126 MHz, Chloroform-d): δ 195.1, 159.1, 156.2, 142.0, 136.5, 134.1, 131.1, 130.8, 128.7, 128.5, 128.2, 128.0, 125.3, 124.9, 124.1, 122.7, 121.8, 106.7, 55.7 (IV-4 is consistent with the reported structure in the literature. The literature is as follows, Leifert, D.; Daniliuc, C.G.; Studer, A. Org. Lett. 2013, 15, 6286–6289).

[0087] Upon verification, the obtained compound is the compound shown in Formula IV-4.

[0088] Example 5

[0089] Synthesize the compound shown in Formula IV-5

[0090] According to Figure 1 the synthetic route map shown, synthesize the compound shown in Formula IV-5. The specific steps are as follows:

[0091] Add the pre-dried 10 mL reaction tube under nitrogen protection with the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-5 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). Stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp at 45 °C. Then perform vacuum distillation on the reaction mixture. After concentration, perform silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1. After collection, perform vacuum distillation to obtain the product), so as to obtain the compound shown in Formula IV-5.

[0092]

[0093] The experimental data for structure verification are as follows:

[0094] A white solid (21.0 mg, 0.059 mmol, yield 39%). Melting point: 155–156 °C. 1 HNMR (500 MHz, Chloroform-d): δ 8.76 (d, J = 8.6 Hz, 1H), 8.68–8.62 (m, 1H), 8.34 (d, J = 1.9 Hz, 1H), 8.25–8.18 (m, 1H), 8.13 (dd, J = 8.6, 1.9 Hz, 1H), 8.06 (dd, J = 8.3, 1.4 Hz, 2H), 7.82–7.72 (m, 2H), 7.69–7.58 (m, 3H), 7.44–7.49 (m, 4H), 7.40–7.35 (m, 1H). 1313C NMR (126 MHz, Chloroform-d): δ 194.9, 157.6, 142.7, 140.8, 140.0, 136.3, 134.2, 132.4, 131.0, 130.8, 130.7, 129.2, 129.1, 128.7, 128.5, 128.1, 127.6, 125.3, 124.5, 124.4, 123.1, 122.3. IR (ATR): 2920, 1666, 1177, 890, 823, 746, 681 cm -1 . HRMS (ESI) m / z: [M+Na] + calcd. for C 26 H 17 NONa + 382.1202, found 382.1204。

[0095] It was verified that the obtained compound was the compound shown in Formula IV-5.

[0096] Example 6

[0097] Synthesize the compound shown in Formula IV-6

[0098] According to Figure 1 the synthetic route diagram shown, synthesize the compound shown in Formula IV-6. The specific steps are as follows:

[0099] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-6 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), acetonitrile (1.5 mL). Under the condition of 45 °C, stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp. Then carry out vacuum distillation on the reaction mixture. After concentration, carry out silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1. After collection, carry out vacuum distillation to obtain the product), so as to obtain the compound shown in Formula IV-6.

[0100]

[0101] The experimental data for structure verification are as follows:

[0102] A white solid (24.8 mg, 0.083 mmol, yield 55%). 11H NMR (500 MHz, Chloroform-d): δ 8.71 (dd, J = 9.1, 5.2 Hz, 1H), 8.63–8.55 (m, 1H), 8.24–8.17 (m, 1H), 8.08–7.99 (m, 2H), 7.85 (dd, J = 9.4, 2.6 Hz, 1H), 7.81–7.75 (m, 2H), 7.62–7.64 (m, 2H), 7.53–7.44 (m, 2H). 13 13C NMR (126 MHz, Chloroform-d): δ 194.3, 161.7 (d, J = 252.0 Hz), 156.2, 142.4, 136.1, 134.2, 131.1, 131.0, 130.2, 129.0 (d, J = 33.5 Hz), 128.9, 128.7, 125.1 (d, J = 8.4 Hz), 124.3, 122.1, 120.9, 120.7, 112.1 (d, J = 22.3 Hz) (IV-6 is consistent with the reported structure in the literature. The literature is as follows, Leifert, D.; Daniliuc, C.G.; Studer, A. Org. Lett. 2013, 15, 6286–6289).

[0103] It was verified that the obtained compound was the compound shown in Formula IV-6.

[0104] Example 7

[0105] Synthesize the compound shown in Formula IV-7

[0106] According to Figure 1 The synthetic route diagram shown, synthesize the compound shown in Formula IV-7. The specific steps are as follows:

[0107] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-7 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), acetonitrile (1.5 mL). Under the condition of 45 °C, stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp. Then carry out vacuum distillation on the reaction mixture, concentrate and carry out silica gel column chromatography separation (stationary phase for column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1, collect and carry out vacuum distillation to obtain the product), to obtain the compound shown in Formula IV-7.

[0108]

[0109] The experimental data for structure verification are as follows:

[0110] A white solid (28.6 mg, 0.090 mmol, yield 60%). 1 1H NMR (500 MHz, Chloroform-d): δ 8.64 (d, J = 8.9 Hz, 1H), 8.61–8.57 (m, 1H), 8.23–8.15 (m, 2H), 8.04 (dd, J = 8.4, 1.4 Hz, 2H), 7.83 (dd, J = 8.9, 2.2 Hz, 1H), 7.81–7.75 (m, 2H), 7.62–7.66 (m, 1H), 7.52–7.47 (m, 2H). 13 13C NMR (126 MHz, Chloroform-d): δ 194.2, 156.1, 142.6, 136.1, 134.3, 134.1, 132.1, 131.9, 131.1, 131.0, 129.6, 128.9, 128.8, 126.7, 124.8, 124.2, 124.1, 122.2 (IV-7 is consistent with the reported structure in the literature. The literature is as follows, Leifert, D.; Daniliuc, C.G.; Studer, A. Org. Lett. 2013, 15, 6286–6289).

[0111] It was verified that the obtained compound was the compound shown in Formula IV-7.

[0112] Example 8

[0113] Synthesize the compound shown in Formula IV-8

[0114] According to Figure 1 the synthetic route diagram shown, synthesize the compound shown in Formula IV-8. The specific steps are as follows:

[0115] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-8 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), acetonitrile (1.5 mL), and stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp at 45 °C. Then perform vacuum distillation on the reaction mixture, concentrate and perform silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1, collect and perform vacuum distillation to obtain the product), to obtain the compound shown in Formula IV-8.

[0116]

[0117] A white solid (32.6 mg, 0.090 mmol, yield 60%). Melting point: 222–223 °C. 1 1H NMR (500 MHz, Chloroform-d): δ 8.61–8.53 (m, 2H), 8.33 (d, J = 2.0 Hz, 1H), 8.19 (dd, J = 7.7, 1.8 Hz, 1H), 8.04 (dd, J = 8.2, 1.4 Hz, 2H), 7.96 (dd, J = 8.9, 2.0 Hz, 1H), 7.75–7.81 (m, 2H), 7.69–7.61 (m, 1H), 7.7–7.50 (m, 2H). 13 13C NMR (126 MHz, Chloroform-d): δ 194.2, 156.0, 142.6, 136.1, 134.7, 134.3, 132.2, 131.1, 131.0, 129.8, 129.7, 128.9, 128.8, 125.1, 124.3, 124.1, 122.19, 122.16. IR (ATR): 1658, 1248, 1180, 894, 761 cm -1 . HRMS (ESI) m / z: [M+Na] + calcd. for C 20 H 12 BrNONa + 383.9995, found 383.9999.

[0118] Verified that the obtained compound is the compound shown in Formula IV-8.

[0119] Example 9

[0120] Synthesize the compound shown in Formula IV-9

[0121] According to Figure 1 The synthetic route diagram shown, synthesize the compound shown in Formula IV-9, and the specific steps are as follows:

[0122] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-9 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), acetonitrile (1.5 mL), and stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp at 45 °C. Then perform vacuum distillation on the reaction mixture, concentrate and perform silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1, collect and perform vacuum distillation to obtain the product), to obtain the compound shown in Formula IV-9.

[0123]

[0124] A white solid (29.0 mg, 0.098 mmol, yield 65%). 1 H NMR (500 MHz, Chloroform-d): δ 8.69 (d, J = 8.4 Hz, 1H), 8.42 (d, J = 2.0 Hz, 1H), 8.14 (dd, J = 8.3, 1.2 Hz, 1H), 8.10 (d, J = 8.3 Hz, 1H), 8.04 (dd, J = 8.2, 1.4 Hz, 2H), 7.85–7.88 (m, 1H), 7.68–7.57 (m, 3H), 7.48–7.45 (m, 2H), 2.66 (s, 3H). 13 C NMR (126 MHz, Chloroform-d): δ 195.1, 156.6, 141.1, 138.5, 136.4, 134.0, 133.14, 131.1, 131.0, 130.5, 128.7, 127.8, 127.4, 124.5 124.1, 122.4, 121.9, 22.3. (IV-9 is consistent with the reported structure in the literature as follows, Liu, J.; Fan, C.; Yin, H.; Qin, C.; Zhang, G.; Zhang, X.; Yi, H.; Lei, A. Chem. Commun. 2014, 50, 2145–2147.).

[0125] It was verified that the obtained compound was the compound shown in formula IV-9.

[0126] Example 10

[0127] Synthesize the compound shown in formula IV-10

[0128] According to Figure 1 The synthetic route diagram shown, synthesize the compound shown in formula IV-10, and the specific steps are as follows:

[0129] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in formula II-1 (0.3 mmol), the compound shown in formula III-10 (0.15 mmol), the catalyst shown in formula I (0.03 mmol), acetonitrile (1.5 mL), and stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp at 45 °C. Then perform vacuum distillation on the reaction mixture, concentrate it, and perform silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 20:1, collect and perform vacuum distillation to obtain the product), to obtain the compound shown in formula IV-10.

[0130]

[0131] A white solid (20.2 mg, 0.065 mmol, yield 43%). Melting point: 172–173 °C. 1 HNMR (500 MHz, Chloroform-d): δ 8.63 (d, J = 8.4 Hz, 1H), 8.20–8.16 (m, 1H), 8.12 (d, J = 9.0 Hz, 1H), 8.05–8.01 (m, 2H), 7.96 (d, J = 2.8 Hz, 1H), 7.85 - 7.88 (m, 1H), 7.69 - 7.66 (m, 1H), 7.63–7.59 (m, 1H), 7.48–7.45 (m, 2H), 7.40 (dd, J = 9.0, 2.7 Hz, 1H), 4.05 (s, 3H). 13 CNMR (126 MHz, Chloroform-d): δ 195.1, 159.6, 154.8, 138.0, 136.6, 134.0, 132.9, 132.3, 131.0, 130.9, 128.7, 128.1, 127.5, 126.0, 124.2, 122.4, 119.3, 103.0, 55.9. IR (ATR): 2987, 2901, 2027, 1406, 1242, 1066, 892 cm -1 .HRMS (ESI) m / z: [M+Na] + calcd. for C 21 H 15 NO2Na + 336.0995, found 336.0997.

[0132] It was verified that the obtained compound was the compound shown in Formula IV-10.

[0133] Example 11

[0134] Synthesize the compound shown in Formula IⅤ-11

[0135] According to Figure 1 the synthetic route diagram shown, synthesize the compound shown in Formula IV-11. The specific steps are as follows:

[0136] Add a pre-dried 10 mL reaction tube under nitrogen protection with the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-11 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). Stir overnight (12 h) under irradiation of a 38 W blue LED (450 nm) lamp at 45 °C. Then perform vacuum distillation on the reaction mixture. After concentration, perform silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1. After collection, perform vacuum distillation to obtain the product) to obtain the compound shown in Formula IV-11.

[0137]

[0138] A white solid (24.8 mg, 0.083 mmol, yield 55%). 1 1H NMR (500 MHz, Chloroform-d): δ 8.59 (d, J = 8.3 Hz, 1H), 8.28–8.14 (m, 3H), 8.03 (dd, J = 8.4, 1.4 Hz, 2H), 7.91 (dd, J = 8.3, 7.0 Hz, 1H), 7.71 (dd, J = 8.2, 7.0, Hz, 1H), 7.66–7.61 (m, 1H), 7.55–7.46 (m, 3H). 13 13C NMR (126 MHz, Chloroform-d) δ 194.7, 162.2 (d, J = 249.5 Hz), 156.8, 139.6, 136.3, 134.2, 133.16 (d, J = 9.3 Hz), 132.9 (d, J = 3.8 Hz) 131.5, 131.0, 128.8, 128.6, 127.6, 126.2 (d, J = 10.1 Hz), 123.99, 122.64, 118.3 (d, J = 24.5 Hz), 107.4 (d, J = 23.5 Hz). HRMS (ESI) m / z: [M+Na] + calcd. for C 20 H 12 FNO Na + 324.0795, found 324.0796.

[0139] It was verified that the obtained compound was the compound shown in Formula Ⅳ-11.

[0140] Example 12

[0141] Synthesize the compound shown in Formula IV-12

[0142] According to Figure 1The compound shown in Formula IV-12 was synthesized according to the synthetic route diagram shown below. The specific steps are as follows:

[0143] A pre-dried 10 mL reaction tube was charged under nitrogen protection with the compound shown in Formula II-1 (0.3 mmol), the compound shown in Formula III-12 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). The mixture was stirred overnight (12 h) at 45 °C under irradiation with a 38 W blue LED (450 nm) lamp. Then, the reaction mixture was distilled under reduced pressure, concentrated, and separated by silica gel chromatography (stationary phase for column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1). After collection, distillation under reduced pressure was carried out to obtain the product, i.e., the compound shown in Formula IV-12.

[0144]

[0145] A white solid 14 (27.2 mg, 0.086 mmol, yield 57%). Melting point: 185–186 °C. 1 1H NMR (500 MHz, Chloroform-d): δ 8.64 (d, J = 8.3 Hz, 1H), 8.61 (d, J = 2.3 Hz, 1H), 8.15 (dd, J = 8.4, 4.2 Hz, 2H), 8.05–7.99 (m, 2H), 7.91–7.94 (m, 1H), 7.76–7.68 (m, 2H), 7.62–7.66 (m, 1H), 7.51–7.47 (m, 2H). 13 13C NMR (126 MHz, Chloroform-d): δ 194.7, 157.8, 141.2, 136.1, 134.4, 134.3, 132.5, 132.2, 131.7, 130.9, 129.9, 128.8, 128.7, 127.6, 125.7, 124.1, 122.5, 122.0. IR (ATR): 2971, 2902, 1660, 1408, 1241, 1056, 893, 825, 757, 675 cm - 1 . HRMS (ESI) m / z: [M+Na] + calcd. for C 20 H 12 ClNONa + 340.0500, found 340.0504.

[0146] It was verified that the obtained compound was the compound shown in Formula IV-12.

[0147] Example 13

[0148] Synthesize the compound shown in Formula IV-13

[0149] According to Figure 1 The synthetic route diagram shown, synthesize the compound shown in Formula IV-13, and the specific steps are as follows:

[0150] Add the pre-dried 10 mL reaction tube under nitrogen protection with the compound shown in Formula II-2 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). Stir overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp at 45 °C. Then perform vacuum distillation on the reaction mixture, concentrate it, and perform silica gel column chromatography separation (stationary phase for column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1, collect and perform vacuum distillation to obtain the product) to obtain the compound shown in Formula IV-13.

[0151]

[0152] A white solid (34.7 mg, 0.117 mmol, yield 78%). 1 H NMR (500 MHz, Chloroform-d): δ8.71 (d, J = 8.4 Hz, 1H), 8.64 (dd, J = 8.0, 1.6 Hz, 1H), 8.21 (dd, J = 7.9, 1.6 Hz, 1H), 8.15–8.08 (m, 1H), 7.95–7.91 (m, 2H), 7.86 - 7.90 (m, 1H), 7.81–7.74 (m, 2H), 7.63 - 7.66 (m, 1H), 7.27 (d, J = 8.2 Hz, 2H), 2.42 (s, 3H). 13 C NMR (126 MHz, Chloroform-d): δ194.7, 158.0, 145.3, 142.8, 133.8, 133.4, 131.4, 131.1, 130.7, 129.5, 129.2, 128.2, 127.9, 127.5, 124.6, 123.9, 122.4, 122.3, 22.0 (The structure of IV-13 is consistent with the literature report. The literature is as follows, Nie, Z.; Ding, Q.; Peng, Y. Tetrahedron 2016, 72, 8350–8357).

[0153] It was verified that the obtained compound is the compound shown in Formula IV-13.

[0154] Example 14

[0155] Compound shown in Synthesis Formula IV-14

[0156] According to Figure 1 the synthesis route diagram shown, synthesize the compound shown in Synthesis Formula IV-14. The specific steps are as follows:

[0157] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in Formula II-3 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), acetonitrile (1.5 mL). Under the condition of 45 °C, stir overnight (12 h) under the irradiation of a 38 W blue LED (450 nm) lamp. Then carry out vacuum distillation on the reaction mixture. After concentration, carry out silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1, collect and carry out vacuum distillation to obtain the product), so as to obtain the compound shown in Formula IV-14.

[0158]

[0159] A white solid (25.2 mg, 0.081 mmol, yield 54%). Melting point: 185–186 °C. 1 1H NMR (500 MHz, Chloroform-d): δ 8.72 (d, J = 8.4 Hz, 1H), 8.65 (dd, J = 7.9, 1.8 Hz, 1H), 8.24–8.20 (m, 1H), 8.14–8.10 (m, 1H), 7.99–7.93 (m, 2H), 7.87–7.91 (m, 1H), 7.81–7.74 (m, 2H), 7.64–7.67 (m, 1H), 7.30 (d, J = 8.2 Hz, 2H), 2.72 (q, J = 7.6 Hz, 2H), 1.26 (t, J = 7.6 Hz, 3H). 13 13C NMR (126 MHz, Chloroform-d): δ 194.7, 158.0, 151.4, 142.8, 134.0, 133.4, 131.4, 131.2, 130.8, 129.2, 128.3, 128.2, 127.9, 127.5, 124.6, 123.9, 122.4, 122.3, 29.3, 15.3. IR (ATR): 2971, 2850, 1650, 1601, 1251, 890, 814, 712 cm -1 . HRMS (ESI) m / z: [M + H] + calcd. for C 22 H 19 NO +312.1388, found 312.1385。

[0160] It was verified that the obtained compound was the compound shown in Formula IV-14.

[0161] Example 15

[0162] Synthesize the compound shown in Formula IV-15

[0163] According to Figure 1 the synthetic route diagram shown, synthesize the compound shown in Formula IV-15. The specific steps are as follows:

[0164] Add the pre-dried 10 mL reaction tube, under nitrogen protection, add the compound shown in Formula II-4 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), acetonitrile (1.5 mL). Under the condition of 45 °C, stir overnight (12 h) under the irradiation of a 38 W blue LED (450 nm) lamp. Then carry out vacuum distillation on the reaction mixture. After concentration, carry out silica gel column chromatography separation (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1. After collection, carry out vacuum distillation to obtain the product), so as to obtain the compound shown in Formula IV-15.

[0165]

[0166] A white solid (24.4 mg, 0.075 mmol, yield 50%). Melting point: 189–190 °C. 1 HNMR (500 MHz, Chloroform-d): δ 8.72 (d, J = 8.3 Hz, 1H), 8.66 (dd, J = 7.4, 2.1 Hz, 1H), 8.22 (dd, J = 7.7, 1.8 Hz, 1H), 8.13 (d, J = 8.2 Hz, 1H), 7.97 (d, J = 8.1 Hz, 2H), 7.88 - 7.91 (m, 1H), 7.81–7.74 (m, 2H), 7.64 - 7.68 (m, 1H), 7.33 (d, J = 8.2 Hz, 2H), 2.98 (p, J = 6.9 Hz, 1H), 1.27 (d, J = 6.9 Hz, 6H). 1313C NMR(126MHz, Chloroform-d): δ 194.7, 158.0, 156.0, 142.9, 134.1, 133.4, 131.4, 131.3, 130.8, 129.2, 128.2, 127.9, 127.6, 126.9, 124.5, 124.0, 122.4, 122.3, 34.6, 23.8. IR(ATR): 2981, 2855, 1652, 1610, 1250, 895, 814, 715 cm -1 . HRMS(ESI) m / z: [M + H] + calcd. for C 23 H 20 NO + 326.1545, found 326.1550。

[0167] It was verified that the obtained compound was the compound shown in Formula IV-15.

[0168] Example 16. Synthesis of the compound shown in Formula IV-16

[0169] According to Figure 1 the synthetic route diagram shown, the compound shown in Formula IV-16 was synthesized. The specific steps are as follows:

[0170] A pre-dried 10 mL reaction tube was charged under nitrogen protection with the compound shown in Formula II-5 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). The mixture was stirred overnight (12 h) at 45 °C under irradiation with a 38 W blue LED (450 nm) lamp. Then the reaction mixture was subjected to vacuum distillation, and after concentration, silica gel column chromatography was carried out (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 20:1. After collection, vacuum distillation was carried out to obtain the product), so as to obtain the compound shown in Formula IV-16.

[0171]

[0172] A white solid (16.4 mg, 0.053 mmol, yield 35%). 11H NMR (400 MHz, Chloroform-d): δ 8.71 (d, J = 8.4 Hz, 1H), 8.67–8.62 (m, 1H), 8.24–8.19 (m, 1H), 8.12 (d, J = 8.0 Hz, 1H), 8.04–7.98 (m, 2H), 7.91–7.87 (m, 1H), 7.81–7.73 (m, 2H), 7.63–7.67 (m, 1H), 6.94 (d, J = 8.9 Hz, 2H), 3.87 (s, 3H). 13 13C NMR (101 MHz, Chloroform-d): δ 193.6, 164.5, 158.2, 142.9, 133.4, 133.4, 131.4, 130.7, 129.3, 129.2, 128.2, 127.9, 127.6, 124.5, 124.0, 122.4, 122.3, 114.0, 55.7 (Compound ⅠV-16 is consistent with the reported structure in the literature. The literature is as follows: Nie, Z.; Ding, Q.; Peng, Y. Tetrahedron 2016, 72, 8350–8357).

[0173] It was verified that the obtained compound was the compound shown in Formula Ⅳ-16.

[0174] Example 17. Synthesis of the compound shown in Formula IV-17

[0175] According to Figure 1 the synthetic route diagram shown, the compound shown in Formula IV-17 was synthesized. The specific steps are as follows:

[0176] A pre-dried 10 mL reaction tube was charged with the compound shown in Formula II-6 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). Under nitrogen protection, the mixture was stirred overnight (12 h) under irradiation with a 38 W blue LED (450 nm) lamp at 45 °C. Then, the reaction mixture was subjected to vacuum distillation. After concentration, silica gel column chromatography was carried out (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1). After collection and vacuum distillation, the product was obtained to give the compound shown in Formula IV-17.

[0177]

[0178] A white solid (30.3 mg, 0.098 mmol, yield 65%). Melting point: 192–193 °C. 1HNMR(500 MHz, Chloroform-d): δ 8.70 (d, J = 8.6 Hz, 1H), 8.65–8.62 (m, 1H), 8.24–8.21 (m, 1H), 8.09 (d, J = 8.1 Hz, 1H), 7.87 (ddd, J = 8.3, 7.0, 1.3 Hz, 1H), 7.82 (d, J = 1.8 Hz, 1H), 7.79–7.71 (m, 3H), 7.63 (ddd, J = 8.2, 7.0, 1.1 Hz, 1H), 7.21 (d, J = 7.9 Hz, 1H), 2.32 (s, 3H), 2.27 (s, 3H). 13 C NMR(126 MHz, Chloroform-d): δ 195.0, 158.2, 144.1, 142.9, 137.2, 134.2, 133.3, 131.7, 131.3, 130.8, 130.0, 129.2, 128.9, 128.1, 127.9, 127.5, 124.5, 123.9, 122.4, 122.3, 20.3, 19.9. IR(ATR): 2981, 2864, 1650, 1710, 1240, 896, 810, 725 cm -1 . HRMS(ESI) m / z: [M + H] + calcd. for C 22 H 18 NO + 312.1388, found 326.1389。

[0179] Verified, the obtained compound is the compound shown in Formula IV-17.

[0180] Example 18: Synthesis of the compound shown in Formula IV-18

[0181] According to Figure 1 the synthesis route diagram shown, the compound shown in Formula IV-18 was synthesized. The specific steps are as follows:

[0182] A pre-dried 10 mL reaction tube was charged under nitrogen protection with the compound shown in Formula II-7 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). The mixture was stirred overnight (12 h) at 45 °C under irradiation with a 38 W blue LED (450 nm) lamp. Then, the reaction mixture was subjected to vacuum distillation. After concentration, silica gel column chromatography was performed (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1). After collection and vacuum distillation, the product was obtained to give the compound shown in Formula IV-18.

[0183]

[0184] A white solid (34.5 mg, 0.111 mmol, yield 74%). Melting point: 192–193 °C. 1 HNMR (500 MHz, Chloroform-d): δ 8.71 (d, J = 8.4 Hz, 1H), 8.66–8.63 (m, 1H), 8.25–8.21 (m, 1H), 8.09 (d, J = 8.2 Hz, 1H), 7.89 (ddd, J = 8.4, 7.0, 1.3 Hz, 1H), 7.81–7.74 (m, 2H), 7.65 (ddd, J = 8.2, 7.0, 1.1 Hz, 1H), 7.62 (d, J = 1.7 Hz, 2H), 2.32 (s, 6H). 13 C NMR (126 MHz, Chloroform-d): δ 195.6, 158.2, 142.9, 138.5, 136.4, 136.0, 133.4, 131.4, 130.8, 129.2, 128.6, 128.2, 127.9, 127.5, 124.8, 123.9, 122.4, 122.3, 21.3. IR (ATR): 2980, 2864, 1652, 1655, 1242, 885, 820, 725 cm -1 . HRMS (ESI) m / z: [M+H] + calcd. for C 22 H 18 NO + 312.1388, found 326.1385.

[0185] It was verified that the obtained compound was the compound shown in Formula IV-18.

[0186] Example 19

[0187] Synthesize the compound shown in Formula IV-19

[0188] According to Figure 1 the synthetic route diagram shown, synthesize the compound shown in Formula IV-19. The specific steps are as follows:

[0189] A pre-dried 10 mL reaction tube was charged, under nitrogen protection, with the compound shown in Formula II-8 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). The mixture was stirred overnight (12 h) at 45 °C under irradiation with a 38 W blue LED (450 nm) lamp. Then, the reaction mixture was subjected to distillation under reduced pressure. After concentration, silica gel column chromatography was carried out (stationary phase of column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1). After collection, distillation under reduced pressure was performed to obtain the product, i.e., the compound shown in Formula IV-19.

[0190]

[0191] A white solid 22 (20.0 mg, 0.060 mmol, yield 40%). 1 1H NMR (500 MHz, Chloroform-d): δ 9.26–9.19 (m, 1H), 8.75 (d, J = 8.4 Hz, 1H), 8.67 (dd, J = 6.3, 3.4 Hz, 1H), 8.28–8.24 (m, 1H), 8.19–8.15 (m, 1H), 8.08 (d, J = 8.2 Hz, 1H), 7.96 (d, J = 8.2 Hz, 1H), 7.93–7.90 (m, 1H), 7.79–7.72 (m, 4H), 7.70–7.66 (m, 1H), 7.62 (ddd, J = 8.1, 6.9, 1.2 Hz, 1H), 7.39 (dd, J = 8.2, 7.2 Hz, 1H). 13 13C NMR (126 MHz, Chloroform-d): δ 197.4, 159.1, 143.0, 134.7, 134.5, 134.3, 133.5, 133.2, 131.7, 131.4, 130.9, 129.2, 128.9, 128.8, 128.3, 128.1, 127.6, 126.9, 126.5, 124.7, 124.5, 124.3, 122.5, 122.3 (The structure of IV-19 is consistent with the literature report. The literature is as follows: Cheng, P; Qing, Z; Liu, S; Liu, W; Xie, H; Zeng, J. Tetrahedron Lett. 2014, 55, 6647 - 6651).

[0192] It was verified that the obtained compound was the compound shown in Formula IV-19.

[0193] Example 20: Synthesis of the compound shown in Formula IV-20

[0194] According toFigure 1 The compound shown in Formula IV-20 was synthesized according to the synthetic route diagram shown below. The specific steps are as follows:

[0195] A pre-dried 10 mL reaction tube was charged under nitrogen protection with the compound shown in Formula II-9 (0.3 mmol), the compound shown in Formula III-1 (0.15 mmol), the catalyst shown in Formula I (0.03 mmol), and acetonitrile (1.5 mL). The mixture was stirred overnight (12 h) at 45 °C under irradiation with a 38 W blue LED (450 nm) lamp. Then, the reaction mixture was subjected to vacuum distillation. After concentration, silica gel column chromatography was performed (stationary phase for column chromatography: SiO2, mobile phase: petroleum ether / ethyl acetate = 50:1). The product was obtained after collection and vacuum distillation to obtain the compound shown in Formula IV-20.

[0196]

[0197] A white solid (13.0 mg, 0.045 mmol, yield 30%). 1 1H NMR (500 MHz, Chloroform-d): δ 8.69 (d, J = 9.0 Hz, 1H), 8.65–8.62 (m, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.29–8.25 (m, 1H), 7.93 (dd, J = 3.8, 1.2 Hz, 1H), 7.89 (ddd, J = 8.3, 7.0, 1.3 Hz, 1H), 7.81–7.75 (m, 3H), 7.70 (ddd, J = 8.2, 7.0, 1.1 Hz, 1H), 7.16 (dd, J = 4.9, 3.9 Hz, 1H). 13 13C NMR (126 MHz, Chloroform-d): δ 186.3, 155.7, 142.7, 142.5, 136.9, 136.4, 133.6, 131.4, 130.8, 129.3, 128.7, 128.3, 128.1, 127.7, 125.0, 123.6, 122.3 (The structure of IV-20 is consistent with the reported literature. The literature is as follows: Zhang, X-Y; Weng, W-Z; Liang, H; Yang, H; Zhang, B. Org Lett. 2018, 20, 4686-4690).

[0198] It was verified that the obtained compound was the compound shown in Formula IV-20.

[0199] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. An organic photocatalytic synthesis method of a phenanthridine heterocyclic carbonyl compound, characterized in that, Comprising the following steps: 1) Dissolve the organic photocatalyst and the compounds shown in Formula II and Formula III in a solvent to obtain a reaction solution to be reacted; The organic photocatalyst has the structural formula shown in Formula I: ； 2) Perform an addition reaction on the reaction solution to be reacted obtained in step 1) under blue light to obtain a phenanthridine heterocyclic carbonyl compound; The structural formulas of Formula II and Formula III are: ； In Formula II, Ar is an aromatic ring; R in the formula III 1 is any one of monosubstituted or polysubstituted alkyl, halogen, and methoxy, and R 2 is any one of monosubstituted or polysubstituted alkyl, halogen, and methoxy; The structural formula of the phenanthridine heterocyclic carbonyl compound is shown in Formula IV: ； wherein, R 1 is any one of a mono-substituted or multi-substituted alkyl group, a halogen, and a methoxy group, and R 2 is any one of a mono-substituted or multi-substituted alkyl group, a halogen, and a methoxy group; In step 1), the molar ratio of the organic photocatalyst to the compounds shown in Formula II and Formula III is 0.03:0.3:0.15; The solvent in step 1) is acetonitrile, and the concentration of the compound shown in Formula III in the reaction solution to be reacted is 0.1 mol / L; The wavelength of the blue light in step 2) is 450 nm; The conditions for the addition reaction in step 2) include: the temperature is 40 - 50 °C, and the time is 12 h.

2. The organic photocatalytic synthesis method according to claim 1, characterized in that The compound shown in Formula IV is any one of the following compounds: 。 3. The organic photocatalytic synthesis method according to claim 1, characterized in that The compound shown in Formula II is any one of the compounds shown in Formula II-1 to Formula II-9 below: 。 4. The organic photocatalytic synthesis method according to claim 1, characterized in that, The compound shown in Formula III is any one of the following compounds: 。

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