A method for photo-driven regioselective C6 acylation of purine nucleoside compounds

Abstract

The invention discloses a method for light-driven regioselective C6 acylation of purine nucleoside compounds, and belongs to the technical field of organic synthetic chemistry. The specific steps are: placing a purine nucleoside compound, an aldehyde compound, tert-butyl hydroperoxide, trifluoroacetic acid and anhydrous magnesium sulfate in a reaction tube and adding ethyl acetate to dissolve them, and placing the reaction tube under blue light for irradiation to obtain a C6 acylated purine nucleoside compound. The invention realizes high regioselective direct C6 acylation of purine nucleoside compounds, which not only has high yield, wide application range of substrates, easy to obtain raw materials, good economy, but also mild reaction conditions and green environmental protection.

Description

Technical Field

[0001] The invention relates to a light-driven regioselective C6-position acylation method for purine nucleoside compounds, and belongs to the field of organic chemical synthesis. Background Art

[0002] In recent years, visible light-driven chemical reactions have increasingly developed into a very powerful tool that can perform various functionalizations under mild reaction conditions. However, most visible light-mediated reaction systems require the addition of photocatalysts, such as ruthenium, iridium complexes, or organic dyes. These photocatalysts often contain toxic heavy metal compounds and are generally expensive. Therefore, from the perspective of environmental protection and economy, it is very necessary to develop a class of visible light-driven chemical reactions without photocatalyst catalysis.

[0003] In addition, as the basic components of nucleic acids, nucleosides play a vital role in life processes and are also crucial to biological systems. At the same time, nucleosides also play an important role in biochemistry, biology, biological probes and pharmaceuticals. Since some nucleosides show strong antibacterial, antifungal and neuroprotective activities after modification, pharmacologists believe that nucleosides are of great significance for the research and development of new drugs, and purine nucleosides are an important branch of nucleosides, and also have outstanding antiviral biological activity.

[0004] In recent years, many chemists have made important contributions to the synthesis of purine nucleosides, but the direct C6-selective acylation of purine nucleosides is extremely challenging. Therefore, it is of great significance to develop some green, economical and mild reaction methods to achieve the direct C6-selective acylation of purine nucleosides. Summary of the invention

[0005] The technical problem solved by the present invention is to provide a light-driven regioselective C6 acylation method for purine nucleoside compounds with high regioselectivity, wide substrate applicability, mild reaction conditions, green environmental protection and simple operation, and good yield.

[0006] To achieve the purpose of the present invention, the following scheme is adopted:

[0007] The reaction equation is:

[0008]

[0009] wherein R1 is selected from acetylribosyl, benzoylribosyl, acetylpyranosyl, acetyldeoxyribosyl, benzyl or ethyl ester, and R2 is selected from C1-5 alkyl, phenyl, substituted phenyl; the substituted phenyl is selected from phenyl substituted by C1-5 alkyl, halogen, hydroxyl, C1-5 alkoxy or phenoxy;

[0010] R1 is preferably acetylribosyl, and R2 is selected from methyl, ethyl, propyl, phenyl or substituted phenyl; the substituted phenyl is selected from phenyl substituted by C1-5 alkyl, halogen, hydroxyl, C1-5 alkoxy or phenoxy;

[0011] The oxidant is tert-butyl hydroperoxide (TBHP), the additive is anhydrous magnesium sulfate (MgSO4), the aldehyde is aliphatic aldehyde and aromatic aldehyde, the acid is trifluoroacetic acid (TFA), and the solvent is ethyl acetate (EA).

[0012] The specific steps include:

[0013] 1) Add purine nucleoside compound 1, aldehyde compound, tert-butyl hydroperoxide, trifluoroacetic acid and anhydrous magnesium sulfate to a quartz reaction tube in sequence, add ethyl acetate to dissolve it, place the reaction tube under blue light for irradiation, and stir to obtain C6-acylated purine nucleoside compound 3.

[0014] 2) After the reaction is completed, saturated sodium bicarbonate is added to quench the reaction, extracted with ethyl acetate, the organic layers are combined, and most of the solvent is distilled off under reduced pressure to obtain a crude product, and the crude product is separated and purified by column chromatography using petroleum ether and ethyl acetate as eluents to obtain the target product.

[0015] The aldehyde compound is selected from aliphatic aldehydes or aromatic aldehyde compounds, preferably C1-5 alkyl aldehydes, benzaldehyde, substituted benzaldehydes; the substituted benzaldehyde is selected from benzaldehyde substituted by C1-5 alkyl, halogen, hydroxyl, C1-5 alkoxy or phenoxy;

[0016] The molar ratio of the purine nucleoside compound, the aldehyde compound, tert-butyl hydroperoxide, trifluoroacetic acid and anhydrous magnesium sulfate is 1:5:2:1.5:3.

[0017] The preferred eluent is: petroleum ether and ethyl acetate in a volume ratio of 1:2 to 1:1.

[0018] The present invention preferably prepares the following purine nucleoside compounds:

[0019]

[0020]

[0021] The technology of the present invention has the following advantages:

[0022] 1) A method for regioselective C6 acylation of purine nucleoside compounds was achieved through visible light-driven Mannich reaction. This method is carried out at room temperature through visible light-driven reaction, and no photocatalyst is used, avoiding the use of toxic heavy metals. It is a mild, green and environmentally friendly reaction type. In addition, the reaction uses cheap and readily available aldehyde compounds as functionalizing agents, which has good economic efficiency, and the reaction has regioselectivity and functional group universality.

[0023] 2) The preparation process of the present invention is simple and efficient, with high yield, and the yield of some target products is more than 83%. The reaction conditions are mild, and the target compounds are easy to separate and purify. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 3aa prepared in Example 1 1 H-NMR nuclear magnetic resonance spectrum;

[0025] Figure 2 3aa prepared in Example 1 13 C-NMR nuclear magnetic resonance spectrum;

[0026] Figure 3 3ab prepared in Example 2 1 H-NMR nuclear magnetic resonance spectrum;

[0027] Figure 4 3ab prepared in Example 2 13 C-NMR nuclear magnetic resonance spectrum;

[0028] Figure 5 3ba prepared in Example 25 1 H-NMR nuclear magnetic resonance spectrum;

[0029] Figure 6 3ba prepared in Example 25 13 C-NMR nuclear magnetic resonance spectrum. DETAILED DESCRIPTION

[0030] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0031] Unless otherwise specified, the raw materials and reagents recorded are commercially available products or prepared by known methods.

[0032] All target compounds were analyzed by NMR ( 1 H, 13 C) Spectral data characterization.

[0033] The yields of the target products in the following examples are all isolated yields.

[0034] Example 1

[0035]

[0036] 1a (0.2 mmol), 4-methylbenzaldehyde 2a (1.0 mmol), tert-butyl hydroperoxide TBHP (0.4 mmol), trifluoroacetic acid TFA (0.3 mmol) and anhydrous MgSO4 (0.6 mmol) were placed in a 20 mL quartz reaction tube, dissolved with ethyl acetate (2 mL) and placed at room temperature for irradiation with blue LED ((wavelength range: 450-470 nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10 mL) was added, and then extracted with ethyl acetate 3 times (3×20 mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3aa with a yield of 82%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.10(s,1H),8.35(s,1H),7.93(d,J=8.2Hz,2H),7.28(d,J=8.2Hz,2H),6.29(d,J=5.2Hz,1 H),6.00(t,J=5.4Hz,1H),5.67(t,J=5.4Hz,1H),4.51–4.35(m,3H),2.42(s,3H),2.15(s,3H),2.11(s,3H),2.08(s,3H); 13 C NMR(101MHz,Chloroform-d)δ190.8,170.3,169.6,169.3,153.8,152.7,152.1,145.3,1 45.0,132.7,132.4,130.9,129.3,86.6,80.5,73.0,70.5,62.9,21.8,20.7,20.5,20.3.

[0037] Example 2

[0038]

[0039] 1a (0.2mmol), benzaldehyde 2b (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ab with a yield of 83%. The characterization data of this compound are as follows: 1 HNMR(400MHz,Chloroform-d)δ9.12(s,1H),8.37(s,1H),8.04(d,J=8.2Hz,2H),7.63(t,J=7.4Hz,1H),7.49((t,J=7.8Hz,2H), 6.30(d,J=5.2Hz,1H),6.01(t,J=5.4Hz,1H),5.67(t,J=5.0Hz,1H),4.55–4.37(m,3H),2.15(s,3H),2.12(s,3H),2.09(s,3H); 13 C NMR(101MHz,Chloroform-d)δ191.1,170.2,169.5,169.3,153.4,152.7,152.1,145. 1,135.1,134.1,132.4,130.7,128.5,86.6,80.5,73.0,70.5,62.9,20.7,20.5,20.3.

[0040] Example 3

[0041]

[0042] 1a (0.2mmol), 4-ethylbenzaldehyde 2c (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ac with a yield of 74%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.11(s,1H),8.35(s,1H),7.97(d,J=8.2Hz,2H),7.32(d,J=8.2Hz,2H),6.30(d,J=5.2Hz,1H),6.01(t,J=5 .4Hz,1H),5.67(t,J=5.2Hz,1H),4.53–4.36(m,3H),2.72(q,J=7.6Hz,2H),2.16(s,3H),2.13(s,3H),2.10(s,3H),1.26(t,J=7.6Hz,3H); 13 C NMR(101MHz,Chloroform-d)δ190.8,170.3,169.6,169.3,153.8,152.7,152.1,151.4,144 .9,132.8,132.4,131.0,128.1,86.6,80.5,73.0,70.5,62.9,29.1,20.7,20.5,20.4,15.0.

[0043] Example 4

[0044]

[0045] 1a (0.2mmol), 4-tert-butylbenzaldehyde 2d (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate = 1 / 2) to obtain a yellow liquid 3ad with a yield of 69%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.11(s,1H),8.37(s,1H),7.98(d,J=8.4Hz,2H),7.50(d,J=8.4Hz,2H),6.30(d,J=5.2Hz,1 H),6.01(t,J=5.4Hz,1H),5.68(t,J=5.0Hz,1H),4.52–4.37(m,3H),2.16(s,3H),2.12(s,3H),2.09(s,3H),1.33(s,9H); 13 C NMR(101MHz,Chloroform-d)δ190.8,170.3,169.6,169.3,158.1,153.7,152.7,152.1,145 .0,132.5,132.3,130.7,125.6,86.6,80.5,73.0,70.5,62.9,35.2,31.0,20.7,20.5,20.4.

[0046] Example 5

[0047]

[0048] 1a (0.2mmol), 4-fluorobenzaldehyde 2e (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ae with a yield of 47%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.12(s,1H),8.37(s,1H),8.15–8.10(m,2H),7.21–7.12(m,2H),6.29(d,J=5.2H z,1H),6.00(t,J=5.2Hz,1H),5.67(t,J=5.4Hz,1H),4.52–4.37(m,3H),2.16(s,3H),2.12(s,3H),2.09(s,3H); 13 C NMR(101MHz,Chloroform-d)δ189.4,170.2,169.6,169.3,166.4(d,J=257.0Hz),153.0,152.8,152.0,145.2,133 .6(d,J=9.6Hz),132.5,131.5(d,J=2.8Hz),115.8(d,J=22.0Hz),86.7,80.5,73.0,70.4,62.9,20.7,20.5,20.4.

[0049] Example 6

[0050]

[0051] 1a (0.2mmol), 4-chlorobenzaldehyde 2f (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3af with a yield of 51%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.13(s,1H),8.44(s,1H),8.03(d,J=8.6Hz,2H),7.48(d,J=8.0Hz,2H),6.31(d,J=5 .0Hz,1H),6.01(t,J=5.4Hz,1H),5.67(t,J=5.2Hz,1H),4.54–4.40(m,3H),2.17(s,3H),2.14(s,3H),2.11(s,3H); 13 C NMR(101MHz,Chloroform-d)δ189.8,170.2,169.5,169.3,152.9,152.6,152.0,145. 3,140.7,133.5,132.5,132.1,128.9,86.7,80.5,73.0,70.4,62.9,20.7,20.5,20.3.

[0052] Example 7

[0053]

[0054] 1a (0.2mmol), 4-bromobenzaldehyde 2g (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ag with a yield of 58%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.13(s,1H),8.39(s,1H),7.99–7.94(m,2H),7.68–7.64(m,2H),6.30(d,J=5.2Hz,1H),6.00( t,J=5.4Hz,1H),5.69–5.65(m,1H),4.53–4.49(m,1H),4.44(dd,J=15.4,3.8Hz,2H),2.17(s,3H),2.13(s,3H),2.10(s,3H); 13 C NMR(101MHz,Chloroform-d)δ190.1,170.3,169.6,169.4,152.9,152.5,152.1,145. 4,133.9,132.2,131.9,131.6,129.7,86.7,80.5,73.0,70.5,62.9,20.8,20.5,20.4.

[0055] Example 8

[0056]

[0057] 1a (0.2mmol), 4-hydroxybenzaldehyde 2h (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ah with a yield of 43%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.11(s,1H),8.43(s,1H),7.74(d,J=8.4Hz,2H),6.71(d,J=8.8Hz,2H),6.31(d,J=5 .2Hz,1H),6.01(t,J=5.4Hz,1H),5.67(t,J=5.2Hz,1H),4.54–4.39(m,3H),2.16(s,3H),2.12(s,3H),2.11(s,3H); 13 C NMR(101MHz,Chloroform-d)δ189.2,170.4,169.6,169.4,162.6,154.8,152.4,152. 2,144.9,133.3,131.5,127.2,115.9,86.8,80.5,73.0,70.4,62.9,20.8,20.5,20.4.

[0058] Example 9

[0059]

[0060] 1a (0.2mmol), 4-methoxybenzaldehyde 2i (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ai with a yield of 64%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.12(s,1H),8.34(s,1H),8.13–8.02(m,2H),7.07–6.92(m,2H),6.30(d,J=5.4Hz,1H),6. 02(t,J=5.4Hz,1H),5.68(dd,J=5.5,4.4Hz,1H),4.52–4.39(m,3H),3.89(s,3H),2.17(s,3H),2.14(s,3H),2.11(s,3H); 13 C NMR(101MHz,Chloroform-d)δ189.5,170.2,169.5,169.3,164.4,154.1,152.5,152.1,1 44.8,133.2,132.3,128.1,113.9,86.5,80.4,72.9,70.4,62.9,55.5,20.7,20.5,20.3.

[0061] Example 10

[0062]

[0063] 1a (0.2mmol), 4-ethoxybenzaldehyde 2j (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3aj with a yield of 52%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.10(s,1H),8.34(s,1H),8.03(d,J=8.8Hz,2H),6.94(d,J=8.8Hz,2H),6.29(d,J=5.2Hz,1H),6.00(t,J= 5.4Hz,1H),5.71–5.62(m,1H),4.51–4.36(m,3H),4.11(q,J=7.0Hz,2H),2.16(s,3H),2.12(s,3H),2.09(s,3H),1.43(t,J=7.0Hz,3H); 13 C NMR(101MHz,Chloroform-d)δ189.4,170.3,169.6,169.3,163.9,154.2,152.5,152.1,144 .8,133.3,132.3,127.9,114.3,86.5,80.4,72.9,70.5,63.8,62.9,20.7,20.5,20.4,14.6.

[0064] Embodiment 11

[0065]

[0066] 1a (0.2mmol), 4-butoxybenzaldehyde 2k (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate = 1 / 2) to obtain a yellow liquid 3ak with a yield of 63%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.09(s,1H),8.33(s,1H),8.04–7.96(m,2H),6 .97–6.89(m,2H),6.28(d,J=5.2Hz,1H),6.00(t,J=5.4Hz,1H),5.66(t,J=5.0 Hz,1H),4.49–4.35(m,3H),4.02(t,J=6.4Hz,2H),2.14(s,3H),2.10(s,3H), 2.07(s,3H),1.76(p,J=6.6Hz,2H),1.54–1.40(m,2H),0.95(t,J=7.4Hz,3H); 13 C NMR(101MHz,Chloroform-d)δ189.4,170.2,169.5,169.3,164.1,154.2,152.5,152.0,144.8,13 3.2,132.2,127.8,114.3,86.5,80.4,72.9,70.4,67.9,62.8,30.9,20.7,20.4,20.3,19.0,13.7.

[0067] Example 12

[0068]

[0069] 1a (0.2mmol), 4-phenoxybenzaldehyde 2l (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3al with a yield of 60%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.10(s,1H),8.35(s,1H),8.05(d,J=8.8Hz,2H),7.43–7.35(m,2H),7.20(t,J=7.4Hz,1H),7.08(d,J=7.4Hz,2H),7 .01(d,J=8.8Hz,2H),6.30(d,J=5.2Hz,1H),6.00(t,J=5.4Hz,1H),5.72 –5.61(m,1H),4.53–4.37(m,3H),2.16(s,3H),2.12(s,3H),2.09(s,3H); 13 C NMR(101MHz,Chloroform-d)δ189.5,170.3,169.6,169.3,163.1,155.0,153.7,152.7,152.1,144. 9,133.2,132.4,130.1,129.5,124.9,120.4,117.1,86.6,80.5,73.0,70.5,62.9,20.8,20.5,20.4.

[0070] Example 13

[0071]

[0072] 1a (0.2mmol), 2-methylbenzaldehyde 2m (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate = 1 / 2) to obtain a yellow liquid 3am with a yield of 32%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.10(s,1H),8.37(s,1H),7.55–7.32(m,3H),7.24(d,J=7.4Hz,1H),6.30(d,J=5.2 Hz,1H),6.01(t,J=5.2Hz,1H),5.68(t,J=5.0Hz,1H),4.55–4.37(m,3H),2.61(s,3H),2.14(s,3H),2.11(s,3H); 13 C NMR(101MHz,Chloroform-d)δ194.0,170.3,169.5,169.3,153.7,152.9,152.2,145.2,140.3,1 35.0,132.6,132.3,132.2,131.9,125.4,86.6,80.5,73.0,70.5,62.9,21.4,20.7,20.5,20.3.

[0073] Embodiment 14

[0074]

[0075] 1a (0.2mmol), 2-fluorobenzaldehyde 2n (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3an with a yield of 43%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.08(s,1H),8.39(s,1H),7.91(td,J=7.4,1.8Hz,1H),7.66–7.56(m,1H),7.32(td,J=7.6,1.0Hz,1H),7.11(ddd,J=1 0.2,8.2,1.0Hz,1H),6.30(d,J=5.2Hz,1H),5.99(t,J=5.4Hz,1H),5.68(t ,J=5.0Hz,1H),4.51–4.36(m,3H),2.15(s,3H),2.11(s,3H),2.09(s,3H); 13 C NMR(101MHz,Chloroform-d)δ190.0,170.3,169.6,169.3,161.7(d,J=256.2Hz),153.1,152.4,152.3,145.5,135.4(d,J=8.8Hz),131 .5,131.5(d,J=1.8Hz),125.2(d,J=12.0Hz),124.6(d,J=3.4Hz),116.4(d,J=21.8Hz),86.6,80.5,73.0,70.5,62.9,20.7,20.5,20.4.

[0076] Embodiment 15

[0077]

[0078] 1a (0.2mmol), 2-methoxybenzaldehyde 2o (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate = 1 / 2) to obtain a yellow liquid 3ao with a yield of 56%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.01(s,1H),7.85–7.76(m,1H),7.54(ddd,J=8.6,7.4,1.8Hz,1H),7.09(td,J=7.4,0.8Hz,1H),6.92(d,J=8.2Hz, 1H),6.27(d,J=5.2Hz,1H),5.96(t,J=5.4Hz,1H),5.66(t,J=5.0Hz,1H) ,4.49–4.34(m,3H),3.46(s,3H),2.14(s,3H),2.09(s,3H),2.06(s,3H); 13 CNMR(101MHz,Chloroform-d)δ192.5,170.2,169.5,169.3,159.4,154.4,152.6,152.1,144.7, 134.8,131.1,131.0,126.5,120.9,111.8,86.5,80.3,72.9,70.4,62.8,55.5,20.7,20.4,20.3.

[0079] Example 16

[0080]

[0081] 1a (0.2mmol), 3-methylbenzaldehyde 2p (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ap with a yield of 48%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.11(s,1H),8.34(s,1H),7.81(d,J=1.8Hz,1H),7.72(dd,J=7.8,1.8Hz,1H),7.23(d,J=7.8Hz,1H),6.29(d,J= 5.2Hz,1H),6.01(t,J=5.4Hz,1H),5.68(t,J=5.0Hz,1H),4.53–4.36(m ,3H),2.32(s,3H),2.30(s,3H),2.16(s,3H),2.12(s,3H),2.09(s,3H); 13 C NMR(101MHz,Chloroform-d)δ191.1,170.3,169.6,169.3,154.0,152.6,152.2,144.9,144.2,137 .1,133.0,132.3,131.5,129.8,128.7,86.6,80.4,72.9,70.5,62.9,20.7,20.5,20.4,20.2,19.7.

[0082] Embodiment 17

[0083]

[0084] 1a (0.2mmol), 3-fluorobenzaldehyde 2q (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3aq with a yield of 35%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.14(s,1H),8.40(s,1H),7.88–7.79(m,2H),7.49(td,J=8.0,5.4Hz,1H),7.38–7.32(m,1H),6.31(d,J=5.2 Hz,1H),6.01(t,J=5.4Hz,1H),5.67(dd,J=5.4,4.6Hz,1H),4.53–4.48(m,1H),4.47–4.39(m,2H),2.17(s,3H),2.14(s,3H),2.11(s,3H); 13 C NMR(101MHz,Chloroform-d)δ189.8(d,J=2.2Hz),170.3,169.6,169.3,162.6(d,J=248.0Hz),152.9,152.4,152.0,145.4,137.1(d,J=6.8Hz ), 132.4, 130.2 (d, J = 7.8Hz), 126.8 (d, J = 3.2Hz), 121.2 (d, J = 21.6Hz), 117.3 (d, J = 22.8Hz), 86.7, 80.5, 73.0, 70.5, 62.9, 20.8, 20.5, 20.4.

[0085] Embodiment 18

[0086]

[0087] 1a (0.2mmol), 3-chlorobenzaldehyde 2r (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ar with a yield of 39%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.13(s,1H),8.39(s,1H),8.06(t,J=1.9Hz,1H),7.95(dt,J=7.8,1.3Hz,1H),7.60(ddd,J=8.0,2.2,1.1Hz,1H),7 .44(t,J=7.9Hz,1H),6.30(d,J=5.2Hz,1H),6.00(t,J=5.4Hz,1H),5.72 –5.62(m,1H),4.52–4.38(m,3H),2.16(s,3H),2.12(s,3H),2.09(s,3H); 13 CNMR(101MHz,Chloroform-d)δ189.8,170.3,169.6,169.3,152.9,152.2,152.0,145.4,136. 7,134.8,134.0,132.5,130.6,129.8,128.9,86.7,80.5,73.0,70.4,62.9,20.7,20.5,20.4.

[0088] Embodiment 19

[0089]

[0090] 1a (0.2mmol), 3-bromobenzaldehyde 2s (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3as with a yield of 46%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.14(s,1H),8.40(s,1H),8.23(t,J=1.8Hz,1H),8.01(dt,J=7.8,1.4Hz,1H),7.77(ddd,J=8.0,2.0,1.0Hz,1H),7.3 9(t,J=7.8Hz,1H),6.31(d,J=5.2Hz,1H),6.01(t,J=5.2Hz,1H),5.67(t, J=5.0Hz,1H),4.52–4.39(m,3H),2.17(s,3H),2.14(s,3H),2.11(s,3H); 13 C NMR(101MHz,Chloroform-d)δ189.8,170.4,169.6,169.4,153.0,152.2,152.1,145.5,136. 9,133.6,132.5,130.1,129.5,128.6,122.8,86.7,80.6,73.1,70.5,63.0,20.8,20.6,20.4.

[0091] Embodiment 20

[0092]

[0093] 1a (0.2mmol), 2,4,6-trimethylbenzaldehyde 2t (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate = 1 / 2) to obtain a yellow liquid 3at with a yield of 34%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.07(s,1H),8.46(s,1H),6.91(s,2H),6.29(d,J=5.0Hz,1H),5.98(t,J=5.4Hz,1 H),5.66(t,J=5.2Hz,1H),4.52–4.35(m,3H),2.32(s,3H),2.15(s,3H),2.13(s,6H),2.12(s,3H),2.09(s,3H); 13 C NMR(10MHz,Chloroform-d)δ199.7,170.2,169.5,169.3,153.7,152.6,150.4,146.2,139. 6,136.1,135.0,131.7,128.5,86.7,80.3,73.0,70.3,62.8,21.3,20.7,20.5,20.3,19.7.

[0094] Embodiment 21

[0095]

[0096] 1a (0.2mmol), 3,4-dimethylbenzaldehyde 2u (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate = 1 / 2) to obtain a yellow liquid 3au with a yield of 32%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.11(s,1H),8.34(s,1H),7.75(d,J=2.0Hz,1H),7.54(dd,J=8.4,2.0Hz,1H),6.88(d,J=8.4Hz,1H),6.29(d,J =5.2Hz,1H),6.01(t,J=5.2Hz,1H),5.67(t,J=5.0Hz,1H),4.53–4.36(m,3H),3.95(d,J=1.6Hz,6H),2.16(s,3H),2.13(s,3H),2.10(s,3H); 13 C NMR(101MHz,Chloroform-d)δ189.5,170.2,169.5,169.3,154.4,154.3,152.5,152.1,149.3,144 .8,132.4,128.3,127.2,111.5,109.9,86.6,80.5,73.0,70.5,62.9,56.1,56.1,20.7,20.5,20.4.

[0097] Embodiment 22

[0098]

[0099] 1a (0.2mmol), acetaldehyde 2v (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3av with a yield of 65%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.11(s,1H),8.42(s,1H),6.28(d,J=5.2Hz,1H),5.96(t,J=5.4Hz,1 H),5.64(t,J=5.2Hz,1H),4.50–4.34(m,3H),2.88(s,3H),2.15(s,3H),2.12(s,3H),2.07(s,3H); 13 C NMR (101MHz, Chloroform-d) δ198.7,170.2,169.5,169.3,153.7,152.2,149.2,145.9,131.5,86.6,80.4,73.0,70.4,62.9,27.9,20.7,20.5,20.3.

[0100] Embodiment 23

[0101]

[0102] 1a (0.2mmol), propionaldehyde 2w (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3aw with a yield of 70%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.10(s,1H),8.43(s,1H),6.28(d,J=5.2Hz,1H),5.96(t,J=5.2Hz,1H),5.65(t,J=5 .2Hz,1H),4.50–4.36(m,3H),3.35(q,J=7.2Hz,2H),2.15(s,3H),2.12(s,3H),2.07(s,3H),1.27(t,J=7.2Hz,3H); 13 C NMR(101MHz,Chloroform-d)δ201.3,170.3,169.5,169.3,153.6,152.3,149 .7,145.7,131.4,86.6,80.5,73.0,70.5,62.9,33.7,20.7,20.5,20.3,7.6.

[0103] Embodiment 24

[0104]

[0105] 1a (0.2mmol), butyraldehyde 2x (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate = 1 / 2) to obtain a yellow liquid 3ax with a yield of 79%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.09(s,1H),8.41(s,1H),6.27(d,J=5.2Hz,1H),5.96(t,J=5.4Hz,1H),5.68–5.61( m,1H),4.53–4.36(m,3H),3.30(t,J=7.4Hz,2H),2.23–2.03(m,10H),1.82(q,J=7.4Hz,2H),1.03(t,J=7.4Hz,3H); 13 C NMR(101MHz,Chloroform-d)δ200.8,170.3,169.6,169.3,153.6,152.3,149.7, 145.7,131.5,86.6,80.4,73.0,70.5,62.9,42.0,20.7,20.5,20.3,17.2,13.8.

[0106] Embodiment 25

[0107]

[0108] 1b (0.2mmol), p-methylbenzaldehyde 2a (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ba with a yield of 80%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.13(s,1H),8.27(s,1H),7.94(d,J=8.2Hz,2H),7.30(d,J=8.0Hz,2H),6.19(d,J=5.0Hz,1H),6.06( t,J=5.2Hz,1H),5.44(t,J=5.2Hz,1H),4.38(dt,J=11.6,6.2Hz,1H),2.43(s,3H),2.16(s,3H),2.10(s,3H),1.55(d,J=6.4Hz,3H); 13 C NMR(101MHz,Chloroform-d)δ190.8,169.7,169.4,153.7,152.6,152.1,145.3,1 45.2,132.7,132.5,130.9,129.3,87.0,79.0,74.4,73.0,21.8,20.5,20.4,18.7.

[0109] Embodiment 26

[0110]

[0111] 1c (0.2mmol), p-methylbenzaldehyde 2a (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate = 1 / 2) to obtain a yellow liquid 3ca with a yield of 57%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ8.94(s,1H),8.36(s,1H),8.15–8.08(m,2H), 8.06–7.99(m,2H),7.97–7.89(m,4H),7.64–7.51(m,3H),7.50–7.33(m,6H), 7.31–7.24(m,2H),6.56–6.47(m,2H),6.30(t,J=5.2Hz,1H),4.96(dd,J=12. 2,3.2Hz,1H),4.91–4.84(m,1H),4.73(dd,J=12.2,4.2Hz,1H),2.42(s,3H); 13 C NMR(101MHz,Chloroform-d)δ190.7,166.1,165.3,165.1,153.7,152.7,152.1,145.4,145.2,133.9,133.8,133.5,132.7, 132.4,130.8,129.8,129.8,129.7,129.2,129.2,128.6,128.6,128.6,128.5,128.2,87.2,80.9,73.6,71.4,63.34,21.8.

[0112] Embodiment 27

[0113]

[0114] 1d (0.2mmol), p-methylbenzaldehyde 2a (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3da with a yield of 82%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.12(s,1H),8.31(s,1H),7.93(d,J=8.2Hz,2H),7.28(d,J=8.0Hz,2H),6.13(d,J=9.6Hz,1H),5.88(t,J=2.8Hz ,1H),5.75(dd,J=9.6,2.8Hz,1H),5.27(ddd,J=10.4,6.0,2.8Hz,1H),4.14–4.00(m,2H),2.42(s,3H),2.28(s,3H),2.06(s,3H),1.81(s,3H); 13 CNMR(101MHz,Chloroform-d)δ190.8,169.8,169.3,168.8,153.6,153.2,152.3,145.3, 144.6,132.6,131.8,130.9,129.3,78.7,68.0,67.7,65.7,63.8,21.8,20.8,20.6,20.3.

[0115] Embodiment 28

[0116]

[0117] 1e (0.2mmol), p-methylbenzaldehyde 2a (1.0mmol), tert-butyl hydroperoxide TBHP (0.4mmol), trifluoroacetic acid TFA (0.3mmol) and anhydrous MgSO4 (0.6mmol) were placed in a 20mL quartz reaction tube, dissolved with ethyl acetate (2mL) and placed at room temperature and irradiated with blue LED (wavelength range: 450-470nm) light, and the reaction was stirred for 24 hours. After the reaction was completed, saturated sodium bicarbonate (NaHCO3) aqueous solution (10mL) was added, and then extracted with ethyl acetate 3 times (3×20mL). The extract was washed with saturated brine, dried with anhydrous sodium sulfate (Na2SO4) and distilled under reduced pressure to concentrate the crude product. The crude mixture was purified by flash chromatography (petroleum ether / ethyl acetate=1 / 2) to obtain a yellow liquid 3ea with a yield of 80%. The characterization data of this compound are as follows: 1 H NMR(400MHz,Chloroform-d)δ9.13(s,1H),8.33(s,1H),7.93(d,J=8.2Hz,2H),7.29(d,J=8.0Hz,2H),6.14(d,J=9.6Hz,1H),5.89(d,J=2.8Hz ,1H),5.75(dd,J=9.6,2.8Hz,1H),5.28(ddd,J=10.4,6.0,2.8Hz,1H),4.17–4.00(m,2H),2.42(s,3H),2.28(s,3H),2.06(s,3H),1.82(s,3H); 13 CNMR (101MHz, CDCl3) δ190.9,169.8,169.4,168.8,153.6,153.2,152.3,145.4,144. 7,132.7,130.9,129.3,129.1,78.8,68.1,67.8,65.8,63.8,21.9,20.9,20.6,20.4.

[0118] Although the present invention has been described in detail above by means of general description, specific implementation methods and tests, it is obvious to those skilled in the art that some modifications or improvements may be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A method for photo-driven regioselective C6 acylation of purine nucleoside compounds, characterized in that: The method is implemented by the following steps: placing a purine nucleoside compound 1, a fatty aldehyde or an aromatic aldehyde compound, tert-butyl hydroperoxide, trifluoroacetic acid and anhydrous magnesium sulfate in a reaction tube and adding ethyl acetate to dissolve them, and placing the reaction tube under blue light for irradiation to obtain a C6-acylated purine nucleoside compound 3; wherein R1 is selected from acetylribosyl, benzoylribosyl, acetylpyranosyl, acetyldeoxyribosyl, benzyl or ethyl ester, and R2 is selected from C1-5 alkyl, phenyl, substituted phenyl; the substituted phenyl is selected from phenyl substituted by C1-5 alkyl, halogen, hydroxyl, C1-5 alkoxy or phenoxy; The aliphatic aldehyde or aromatic aldehyde compound is selected from C1-5 alkyl aldehyde, benzaldehyde, substituted benzaldehyde; the substituted benzaldehyde is selected from benzaldehyde substituted by C1-5 alkyl, halogen, hydroxyl, C1-5 alkoxy or phenoxy; The wavelength range of the blue light is 450-470nm.

2. The method for regioselective C6 acylation of purine nucleoside compounds driven by light according to claim 1, characterized in that: Wherein R1 is selected from acetylribosyl, R2 is selected from methyl, ethyl, propyl, phenyl or substituted phenyl; the substituted phenyl is selected from phenyl substituted by C1-5 alkyl, halogen, hydroxyl, C1-5 alkoxy or phenoxy.

3. The method for regioselective C6 acylation of purine nucleoside compounds driven by light according to claim 1, characterized in that: The molar ratio of the purine nucleoside compound, the aldehyde compound, tert-butyl hydroperoxide, trifluoroacetic acid and anhydrous magnesium sulfate is 1:5:2:1.5:

3.

4. The method for regioselective C6 acylation of purine nucleoside compounds according to claim 1 or 2, characterized in that: The C6-acylated purine nucleoside compound is selected from one of the following compounds:

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