A method for synthesizing a phenanthrene compound

Abstract

The present invention relates to the technical field of organic synthesis, and particularly relates to a method for synthesizing a phenanthrene compound. A diaryl ketone A, a difluoroolefin B, an additive and an organic solvent are mixed, and the mixed solution is stirred and reacted under the conditions of light and 0-30 °C, and then separated and purified to obtain the phenanthrene compound. The synthesis method of the present invention realizes the cyclization reaction of the diaryl ketone A and the difluoroolefin B, and directly synthesizes the phenanthrene compound by a one-step method, which is a new reaction mode and provides a simple and efficient method for synthesizing polysubstituted phenanthrene. The synthesis method of the present invention has simple, efficient and mild reaction conditions, and does not require the addition of an additional catalyst. The reaction conditions involved in the synthesis method of the present invention have good functional group tolerance and substrate generality, and can be compatible with various functional groups such as ester groups, halogens, and carbonyl groups, and various straight-chain or branched alkyl groups can also complete the reaction.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to a method for synthesizing phenanthrene compounds. Background Art

[0002] Polycyclic aromatic hydrocarbons (PAHs) usually exhibit interesting optical and electrical properties, have many unique chemical and physical properties, and are extremely important parent materials for photochemical materials. [Tatsuhiro Tsukamoto. Angew. Chem. Int. Ed. 2020, 59, 15249–15253] As a class of compounds widely present in natural products and functional materials, the synthesis of phenanthrene is also a very important research direction. At present, the synthesis of phenanthrene compounds has the disadvantages of high substrate synthesis steps, difficult operation, and poor reaction chemoselectivity. For example, the intramolecular cross-coupling of C-Br bonds and C-H bonds under palladium catalysis. [a) Q. Lin, Angew. Chem. Int. Ed. 2019, 58, 16543–16547; b) A. M. Echavarren, J. Am. Chem. Soc. 2007, 129, 6880-6886]; or acid-catalyzed intramolecular Friedel-Crafts aromatization reaction [a) J. Ichikawa, Chem. Commun., 2019, 55, 9267–9270; b) A. Frstner, Chem. Eur. J. 2004, 10, 4556–4575]. Summary of the Invention

[0003] The purpose of the present invention is to provide a method for synthesizing phenanthrene compounds. Through the cyclization reaction of simple diaryl ketone A and difluoroolefin B under light, the phenanthrene compound can be directly synthesized in one step, which can be applied to the synthesis of various substituted phenanthrenes. Without the need to add an additional catalyst, the reaction conditions are simple, mild, and efficient, and it has good substrate generality and functional group tolerance.

[0004] The solution adopted by the present invention to achieve the purpose is: a method for synthesizing phenanthrene compounds, mixing diaryl ketone A, difluoroolefin B and an organic solvent, stirring and reacting the mixed solution under light and at a temperature of 0-30°C, and then separating and purifying to obtain the phenanthrene compound.

[0005] Preferably, the molecular structural formula of the phenanthrene compound is as follows:

[0006]

[0007] The molecular structural formula of the diaryl ketone A is

[0008] The molecular structural formula of the difluoroolefin B is:

[0009] Among them, R1, R2, R3, R4, R5, and R6 are each independently any one of aryl, alkyl, alkoxy, heteroatom, and hydrogen atom, and they can be the same or different.

[0010] In the diaryl ketone A and difluoroolefin B used in the present invention, the types of R1, R2, R3, R4, R5, and R6 do not affect the occurrence of the cyclization reaction, and any kind of group can be selected for R1, R2, R3, R4, R5, and R6.

[0011] Preferably, the alkyl has 1-20 carbon atoms and is a straight-chain structure, cyclic structure, or branched-chain structure; the alkyl has one or more substituents, and when there are multiple substituents, the substituents can be the same or different, and the positions can be the same or different.

[0012] Preferably, the aryl has one or more substituents; when there are multiple substituents, the substituents can be the same or different.

[0013] Preferably, the organic solvent is at least one of methanol, ethanol, isopropanol, tert-butanol, tetrahydrophenanthrene, 2-methyltetrahydrophenanthrene, diethyl ether, dimethylethyl ether, methyl tert-butyl ether, 1,4-epoxyhexane, 1,3-epoxyhexane, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, saturated alkanes of C 4-12 , fluorinated or chlorinated alkanes of C 3-12 , benzene, toluene, xylene, mesitylene, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetone, N-methylpyrrolidone, acetonitrile, saturated alkyl nitriles of C 3-12 .

[0014] Preferably, the molar ratio between the diaryl ketone A and the difluoroolefin B is 1-4:1; the concentration of the difluoroolefin B in the mixed solution is between 0.1 M and 1 M.

[0015] Preferably, the light source for the illumination is any one of visible light and ultraviolet light. Specifically, the light source for the illumination is any one of white light, blue light, purple light, green light, sunlight, and ultraviolet light, and the power of the light source is between 1 W and 60 W.

[0016] Preferably, the additive is at least one of 2,4,6-collidine, 2,6-lutidine, pyridine, triethylamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), and 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), and the molar ratio of the additive to the difluoroolefin B is 1-3:1.

[0017] Preferably, the separation and purification includes filtration, concentration, recrystallization and column chromatography.

[0018] The present invention has the following advantages and beneficial effects: (1) The synthesis method of the present invention realizes the cyclization reaction of diaryl ketone A and difluoroolefin B, directly synthesizes phenanthrene compounds by a one-step method, which is a new reaction mode and provides a simple and efficient method for synthesizing polysubstituted phenanthrene.

[0019] (2) The synthesis method of the present invention has simple, efficient and mild reaction conditions, and does not require the addition of extra catalysts.

[0020] (3) The reaction conditions involved in the synthesis method of the present invention have good functional group tolerance and substrate generality, and can be compatible with various functional groups such as ester groups, halogens, carbonyl groups, etc., and various straight-chain or branched-chain alkyl groups can also complete this reaction. Detailed implementation mode

[0021] For a better understanding of the present invention, the following examples further illustrate the present invention, but the content of the present invention is not limited to the following examples.

[0022] Example 1:

[0023]

[0024] Add A (84 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), 2,4,6-collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL) into a dry photoreaction tube equipped with a magnetic stir bar. Seal the photoreaction tube, then irradiate it with a 6 W 365 nm LED lamp, and stir the reaction mixture at room temperature for 12 hours. Then turn off the light and concentrate the reaction mixture under reduced pressure. Purify the crude product by silica gel column chromatography (200 - 300 mesh) and elute it with PE / EA (100 / 1 - 50 / 1, v / v) to obtain the target compound G1 (54.7 mg of colorless solid, yield 81%).

[0025] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H).13 13C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0026] Example 2:

[0027]

[0028] To a dry photoreaction tube equipped with a magnetic stir bar, add A (84 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry MeCN (2 mL). Seal the photoreaction tube and then irradiate with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 h. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G1 (50.1 mg of colorless solid, yield 74%).

[0029] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0030] Example 3:

[0031]

[0032] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry toluene (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the light was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G1 (47.3 mg of colorless solid, yield 70%).

[0033] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0034] Example 4:

[0035]

[0036] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), lutidine (45.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G1 (47.3 mg of colorless solid, yield 70%).

[0037] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 1313C NMR(151MHz,CDCl3,25℃)δ149.2,138.3,138.1,137.0,136.0,131.0,130.1,129.8,129.4,129.3,129.1,128.4,128.1,127.0,126.3,125.2,122.6,118.2,35.4,31.7,22.1,21.4.IR(ATR):ν3019,2918,2858,1736,1617,1505,1435,1317,1244,1218,1036,820,730cm 1 .HRMS(APCI,m / z):calcd for C 26 H 27 + (M+H) + :339.2107;found:339.2103.

[0038] Example 5:

[0039]

[0040] To a dry photoreaction tube equipped with a magnetic stir bar were added A(84mg,0.4mmol,2equiv.),B(39.2mg,0.2mmol),pyridine(32mg,0.4mmol,2equiv.) and dry DCM(2mL). The photoreaction tube was sealed and then irradiated with a 6W 365nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography(200 - 300 mesh) and eluted with PE / EA(100 / 1 - 50 / 1,v / v) to give the target compound G1(41.9mg of colorless solid,yield 62%).

[0041] 1 1H NMR(600MHz,CDCl3,25℃)δ8.74–8.65(m,1H),8.61–8.54(m,1H),7.82(dd,J=8.3,4.9Hz,2H),7.69(dd,J=8.3,1.9Hz,1H),7.58(s,1H),7.45–7.42(m,2H),7.35(dd,J=8.4,1.7Hz,1H),7.34–7.30(m,2H),2.65(s,3H),2.48(s,3H),1.53(s,9H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0042] Example 6:

[0043]

[0044] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), DBU (60.3 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G1 (23.1 mg of colorless solid, yield 34%).

[0045] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0046] Example 7:

[0047]

[0048] To a dry photoreaction tube equipped with a magnetic stir bar were added A (84 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 390 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G1 (47.9 mg of colorless solid, yield 71%).

[0049] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 1313C NMR(151MHz,CDCl3,25℃)δ149.2,138.3,138.1,137.0,136.0,131.0,130.1,129.8,129.4,129.3,129.1,128.4,128.1,127.0,126.3,125.2,122.6,118.2,35.4,31.7,22.1,21.4.IR(ATR):ν3019,2918,2858,1736,1617,1505,1435,1317,1244,1218,1036,820,730cm 1 .HRMS(APCI,m / z):calcd for C 26 H 27 + (M+H) + :339.2107;found:339.2103.

[0050] Example 8:

[0051]

[0052] To a dry photoreaction tube equipped with a magnetic stir bar was added A(84mg,0.4mmol,2equiv.),B(34.8mg,0.2mmol),collidine(48.4mg,0.4mmol,2equiv.) and dry DCM(2mL). The photoreaction tube was sealed and then irradiated with a 6W 365nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography(200 - 300 mesh) and eluted with PE / EA(100 / 1 - 50 / 1, v / v) to give the target compound G2(45.1mg of colorless solid, yield 71%).

[0053] 1 1H NMR(600MHz,CDCl3,25℃)δ8.66(s,1H),8.46(s,1H),7.84(d,J = 8.4Hz,1H),7.79(d,J = 8.4Hz,1H),7.56(s,1H),7.54(dd,J = 8.5,2.0Hz,1H),7.42(d,J = 7.7Hz,2H),7.39(dd,J = 8.4,1.7Hz,1H),7.33(d,J = 7.6Hz,2H),2.63(s,3H),2.48(s,3H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 139.1, 137.7, 137.3, 136.7, 132.3, 130.8, 130.2, 130.1, 130.0, 129.9, 129.5, 129.2, 128.9, 127.3, 127.1, 125.9, 122.8, 122.3, 22.1, 21.4. IR (ATR): ν 3022, 2922, 2855, 1736, 1617, 1509, 1435, 1375, 1297, 1200, 1140, 1039, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 22 H 17 Cl + (M) + : 316.1013; found: 316.1011.

[0054] Example 9:

[0055]

[0056] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (43.4 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the light was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G3 (57.4 mg of colorless solid, yield 80%).

[0057] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.83 (d, J = 1.9 Hz, 1H), 8.46 (s, 1H), 7.84 (d, J = 8.3 Hz, 1H), 7.72 (d, J = 8.4 Hz, 1H), 7.67 (dd, J = 8.4, 1.9 Hz, 1H), 7.55 (s, 1H), 7.43–7.41 (m, 2H), 7.39 (dd, J = 8.4, 1.7 Hz, 1H), 7.33 (d, J = 7.7 Hz, 2H), 2.63 (s, 3H), 2.48 (s, 3H). 13CNMR(151MHz, CDCl3, 25℃) δ 139.3, 137.7, 137.3, 136.7, 131.2, 130.5, 130.2, 129.9, 129.9, 129.8, 129.5, 129.2, 128.9, 127.0, 125.9, 125.5, 122.8, 120.5, 22.1, 21.4. IR(ATR): ν 3026, 2918, 2855, 1733, 1617, 1509, 1431, 1371, 1297, 1244, 1043, 820, 726 cm 1 . HRMS(APCI, m / z): calcd for C 22 H 17 Br + (M) + : 360.0508; found: 360.0514.

[0058] Example 10:

[0059]

[0060] To a dry photoreaction tube equipped with a magnetic stir bar, add A (84 mg, 0.4 mmol, 2 equiv.), B (53.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 hours. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G4 (39.3 mg of colorless solid, yield 48%).

[0061] 1 H NMR(600MHz, CDCl3, 25℃) δ 8.71(d, J = 8.2Hz, 1H), 8.57–8.56(m, 1H), 7.87(dd, J = 7.8, 1.4Hz, 1H), 7.83(d, J = 8.4Hz, 1H), 7.64(ddd, J = 8.3, 7.0, 1.5Hz, 1H), 7.61–7.58(m, 2H), 7.44(d, J = 8.0Hz, 2H), 7.37(dd, J = 8.4, 1.7Hz, 1H), 7.33(d, J = 7.7Hz, 2H), 2.63(s, 3H), 2.48(s, 3H). 1313C NMR(151MHz,CDCl3,25℃)δ138.8,138.1,137.1,136.2,131.9,130.8,130.0,129.7,129.3,129.1,128.7,128.3,127.0,126.8,126.6,126.4,122.8,122.6,22.1,21.4.IR(ATR):ν3019,2918,2880,1736,1617,1509,1449,1375,1039,823,745cm 1 .HRMS(APCI,m / z):calcd for C 22 H 17 I + (M) + :408.0370;found:408.0362.

[0062] Example 11:

[0063]

[0064] To a dry photoreaction tube equipped with a magnetic stir bar was added A(84mg,0.4mmol,2equiv.),B(39.6mg,0.2mmol),collidine(48.4mg,0.4mmol,2equiv.) and dry DCM(2mL). The photoreaction tube was sealed and then irradiated with a 6W 365nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography(200 - 300 mesh) and eluted with PE / EA(100 / 1 - 50 / 1,v / v) to give the target compound G5(35.7mg of colorless solid,yield 52%).

[0065] 1 1H NMR(600MHz,CDCl3,25℃)δ9.46–9.43(m,1H),8.66(s,1H),8.20(dd,J = 8.3,1.6Hz,1H),7.90(d,J = 8.3Hz,1H),7.85(d,J = 8.4Hz,1H),7.62(s,1H),7.45–7.42(m,2H),7.40(dd,J = 8.4,1.7Hz,1H),7.34(d,J = 7.7Hz,2H),4.05(s,3H),2.65(s,3H),2.48(s,3H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 167.7, 141.4, 137.6, 137.5, 137.1, 134.8, 131.1, 129.9, 129.4, 129.2, 129.2, 128.8, 128.8, 127.5, 127.2, 126.7, 126.0, 125.3, 123.0, 52.5, 22.1, 21.5. IR (ATR): ν 3011, 2978, 2866, 1718, 1617, 1509, 1435, 1312, 1274, 1230, 1043, 827, 730 cm 1 . HRMS (APCI, m / z): calcd for C 24 H 21 O2 + (M + H) + : 341.1536; found: 341.1535.

[0066] Example 12:

[0067]

[0068] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (34 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the light was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G6 (45.2 mg of colorless solid, yield 72%).

[0069] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.44 (dd, J = 1.9, 1.0 Hz, 1H), 8.05 (d, J = 2.4 Hz, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.77 (d, J = 8.6 Hz, 1H), 7.53 (s, 1H), 7.43–7.41 (m, 2H), 7.34 (dd, J = 8.5, 1.7 Hz, 1H), 7.30 (d, J = 7.6 Hz, 2H), 7.23 (dd, J = 8.7, 2.5 Hz, 1H), 4.03 (s, 3H), 2.61 (s, 3H), 2.45 (s, 3H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 158.4, 138.3, 136.9, 136.4, 135.8, 131.0, 130.2, 130.2, 130.1, 129.5, 129.1, 128.4, 127.0, 126.6, 126.3, 122.7, 117.0, 103.8, 55.7, 22.1, 21.4. IR (ATR): ν 3026, 2918, 2866, 1796, 1751, 1617, 1490, 1431, 1375, 1241, 1185, 1036, 827, 730 cm 1 . HRMS (APCI, m / z): calcd for C 23 H 21 O + (M + H) + : 313.1587; found: 313.1580.

[0070] Example 13:

[0071]

[0072] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (39.6 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G7 (53.1 mg of colorless solid, yield 78%).

[0073] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.33 (d, J = 1.7 Hz, 1H), 8.11 (s, 1H), 7.77 (d, J = 8.3 Hz, 1H), 7.44–7.40 (m, 3H), 7.32–7.27 (m, 4H), 4.42–4.38 (m, 4H), 2.59 (s, 3H), 2.47 (s, 3H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 144.0, 143.8, 138.3, 137.2, 136.9, 135.9, 130.3, 130.1, 129.1, 128.5, 127.6, 127.5, 126.9, 125.6, 125.1, 122.6, 114.3, 109.6, 64.7, 22.1, 21.4. IR (ATR): ν 3019, 2926, 2870, 1733, 1617, 1505, 1457, 1379, 1297, 1244, 1073, 837, 734 cm 1 . HRMS (APCI, m / z): calcd for C 24 H 21 O2 + (M + H) + : 341.1536; found: 341.1530.

[0074] Example 14:

[0075]

[0076] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (40 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G8 (58.2 mg of colorless solid, yield 85%).

[0077] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.37 (d, J = 1.7 Hz, 1H), 8.02 (s, 1H), 7.83 (d, J = 8.4 Hz, 1H), 7.52 (s, 1H), 7.43 (d, J = 7.9 Hz, 2H), 7.33–7.29 (m, 3H), 7.22 (s, 1H), 4.16 (s, 3H), 4.04 (s, 3H), 2.63 (s, 3H), 2.47 (s, 3H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 149.5, 149.3, 138.3, 137.1, 136.9, 135.9, 130.2, 130.1, 129.1, 128.5, 127.4, 127.0 (2C), 125.8, 124.2, 122.2, 108.3, 103.2, 56.2, 56.0, 22.1, 21.4. IR (ATR): ν 3004, 2918, 2855, 1740, 1617, 1509, 1464, 1379, 1248, 1159, 1043, 842, 730 cm 1 . HRMS (APCI, m / z): calcd for C 24 H 23 O2 + (M + H) + : 343.1693; found: 343.1684.

[0078] Example 15:

[0079]

[0080] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (40 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G9 (54.8 mg of colorless solid, yield 80%).

[0081] 1 1H NMR (400 MHz, CDCl3, 25 °C) δ 9.45 (s, 1H), 7.78 (d, J = 8.3 Hz, 1H), 7.50 (s, 1H), 7.42 (d, J = 7.7 Hz, 2H), 7.33–7.27 (m, 3H), 6.88 (d, J = 2.4 Hz, 1H), 6.78 (d, J = 2.5 Hz, 1H), 4.13 (s, 3H), 3.95 (s, 3H), 2.60 (s, 3H), 2.47 (s, 3H). 1313C NMR(151MHz,CDCl3,25℃)δ159.9,158.3,139.9,138.3,137.0,136.0,135.3,131.2,130.0,129.0,128.9,127.6,126.8,126.5,126.5,115.2,101.4,99.3,55.9,55.5,22.5,21.4.IR(ATR):ν2996,2937,2855,1781,1606,1513,1453,1364,1278,1211,1066,827,734cm 1 .HRMS(APCI,m / z):calcd forC 24 H 23 O2 + (M+H) + :343.1693;found:343.1688.

[0082] Example 16:

[0083]

[0084] To a dry photoreaction tube equipped with a magnetic stir bar was added A(84mg,0.4mmol,2equiv.),B(38.8mg,0.2mmol),collidine(48.4mg,0.4mmol,2equiv.) and dry DCM(2mL). The photoreaction tube was sealed and then irradiated with a 6W 365nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography(200 - 300 mesh) and eluted with PE / EA(100 / 1 - 50 / 1,v / v) to give the target compound G10(51.1mg of colorless solid,yield 76%).

[0085] 1 1H NMR(600MHz,CDCl3,25℃)δ8.44(s,1H),8.17(d,J = 2.5Hz,1H),7.82(dd,J = 10.3,8.5Hz,2H),7.55(s,1H),7.42(d,J = 7.9Hz,2H),7.36(dd,J = 8.5,1.7Hz,1H),7.33–7.29(m,3H),4.94(d,J = 2.4Hz,2H),2.63(s,3H),2.60(t,J = 2.4Hz,1H),2.47(s,3H). 13CNMR(151MHz,CDCl3,25℃)δ156.3,138.2,137.0,136.9,136.0,130.8,130.2,130.2,130.1,129.6,129.1,128.5,127.2,127.0,126.2,122.8,117.3,105.8,78.7,75.9,56.3,22.1,21.4.IR(ATR):ν3022,2952,2885,1736,1602,1509,1449,1371,1334,1217,1203,1032,823,734cm 1 .HRMS(APCI,m / z):calcd for C 25 H 21 O + (M+H) + :337.1587;found:337.1585.

[0086] Example 17:

[0087]

[0088] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (44.8 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G11 (37.3 mg of colorless solid, yield 51%).

[0089] 1 H NMR(600MHz,CDCl3,25℃)δ8.45(s,1H),8.09(d,J=2.4Hz,1H),7.83(d,J=8.4Hz,1H),7.78(d,J=8.6Hz,1H),7.54(s,1H),7.43(d,J=7.9Hz,2H),7.35(dd,J=8.4,1.7Hz,1H),7.31(d,J=7.8Hz,2H),7.29–7.24(m,1H),5.65–5.61(m,1H),4.77(d,J=6.8Hz,2H),2.63(s,3H),2.47(s,3H),1.86(t,J=1.6Hz,6H).13 13C NMR (151 MHz, CDCl3, 25 °C) δ 157.7, 138.7, 138.3, 136.9, 136.3, 135.7, 130.9, 130.1, 130.1, 129.5, 129.1, 128.3, 128.2, 127.0, 126.6, 126.3, 122.8, 119.8, 117.5, 105.0, 65.2, 26.1, 22.1, 21.4, 18.5. IR (ATR): ν 3063, 2937, 2885, 1736, 1617, 1509, 1446, 1379, 1244, 1215, 1010, 820, 734 cm 1 . HRMS (APCI, m / z): calcd for C 27 H 27 O + (M + H) + : 367.2056; found: 367.2050.

[0090] Example 18:

[0091]

[0092] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (49.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G12 (59.8 mg of colorless solid, yield 77%).

[0093] R f = 0.47 (PE / EA = 10 / 1 (v / v)). NMR Spectroscopy: 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.45 (s, 1H), 8.19 (d, J = 2.5 Hz, 1H), 7.83 (dd, J = 24.8, 8.5 Hz, 2H), 7.60–7.55 (m, 3H), 7.48–7.43 (m, 4H), 7.40–7.36 (m, 2H), 7.35–7.32 (m, 3H), 5.33 (s, 2H), 2.64 (s, 3H), 2.49 (s, 3H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 157.6, 138.2, 137.1, 136.9, 136.5, 135.8, 131.0, 130.2, 130.2, 130.1, 129.5, 129.1, 128.8, 128.4, 128.2, 127.9, 127.0, 126.8, 126.3, 122.8, 117.4, 105.5, 70.5, 22.1, 21.4. IR (ATR): ν 3026, 2918, 2866, 1729, 1602, 1509, 1453, 1379, 1244, 1218, 1025, 823, 738 cm 1 . HRMS (APCI, m / z): calcd for C 29 H 25 O + (M + H) + : 389.1900; found: 389.1896.

[0094] Example 19:

[0095]

[0096] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (52.8 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G13 (63.6 mg of colorless solid, yield 78%).

[0097] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.43 (s, 1H), 8.15 (d, J = 2.4 Hz, 1H), 7.81 (dd, J = 17.6, 8.5 Hz, 2H), 7.56–7.51 (m, 3H), 7.44–7.41 (m, 2H), 7.36 (dd, J = 8.5, 1.7 Hz, 1H), 7.33–7.29 (m, 3H), 7.15–7.10 (m, 2H), 5.27 (s, 2H), 2.62 (s, 3H), 2.47 (s, 3H). 1313C NMR(151MHz,CDCl3,25℃)δ162.6(d,J=246.4Hz),157.3,138.0,136.8,136.5,135.7,135.0,132.7(d,J=3.0Hz),130.8,130.1,130.0,129.6(d,J=8.2Hz),129.4,129.0,128.3,126.9,126.8,126.1,122.6,117.2,115.6(d,J=21.7Hz),105.3,69.7,22.0,21.3.IR(ATR):ν3026,2918,2862,1733,1602,1509,1438,1375,1244,1207,1025,820,730cm 1 .HRMS(APCI,m / z):calcdfor C 29 H 24 FO + (M+H) + :407.1806;found:407.1800.

[0098] Example 20:

[0099]

[0100] To a dry photoreaction tube equipped with a magnetic stir bar were added A(84mg,0.4mmol,2equiv.),B(64.6mg,0.2mmol),collidine(48.4mg,0.4mmol,2equiv.) and dry DCM(2mL). The photoreaction tube was sealed and then irradiated with a 6W 365nm LED lamp. The reaction mixture was stirred at room temperature for 12 hours. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography(200 - 300 mesh) and eluted with PE / EA(100 / 1 - 50 / 1,v / v) to give the target compound G14(67.2mg of colorless solid,72% yield).

[0101] 1 1H NMR(600MHz,CDCl3,25℃)δ8.42(s,1H),8.14(d,J=2.5Hz,1H),7.81(dd,J=17.8,8.5Hz,2H),7.57–7.54(m,3H),7.45–7.41(m,4H),7.36(dd,J=8.4,1.7Hz,1H),7.33–7.28(m,3H),5.26(s,2H),2.62(s,3H),2.47(s,3H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 157.3, 138.2, 137.0, 136.7, 136.1, 135.9, 131.9, 130.9, 130.3, 130.2, 130.1, 129.6, 129.4, 129.1, 128.5, 127.0, 126.9, 126.2, 122.7, 122.2, 117.3, 105.5, 69.7, 22.1, 21.4. IR (ATR): ν 2970, 2914, 2817, 1722, 1617, 1509, 1438, 1394, 1244, 1218, 1174, 1013, 812, 738 cm 1 . HRMS (APCI, m / z): calcd for C 29 H 24 BrO + (M + H) + : 467.1005; found: 467.1001.

[0102] Example 21:

[0103]

[0104] To a dry photoreaction tube equipped with a magnetic stir bar was added A (84 mg, 0.4 mmol, 2 equiv.), B (43.6 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G15 (43.9 mg of colorless solid, yield 61%).

[0105] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.55 (d, J = 8.8 Hz, 1H), 8.49 (d, J = 1.6 Hz, 1H), 8.00 (d, J = 2.1 Hz, 1H), 7.83 (d, J = 8.3 Hz, 1H), 7.70 (dd, J = 8.8, 2.1 Hz, 1H), 7.50 (s, 1H), 7.43–7.40 (m, 2H), 7.38 (dd, J = 8.4, 1.7 Hz, 1H), 7.33 (d, J = 7.7 Hz, 2H), 2.62 (s, 3H), 2.48 (s, 3H). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 140.1, 137.6, 137.4, 136.8, 133.4, 130.7, 130.5, 129.9, 129.4, 129.2, 129.2, 128.7, 128.4, 127.2, 125.4, 124.5, 122.7, 120.7, 22.10, 21.4. IR (ATR): ν 3022, 2918, 2858, 1688, 1613, 1509, 1431, 1371, 1241, 1203, 1036, 823, 730 cm 1 . HRMS (APCI, m / z): calcd for C 22 H 17 Br + (M) + : 360.0508; found: 360.0506.

[0106] Example 22:

[0107]

[0108] To a dry photoreaction tube equipped with a magnetic stir bar was added A (95.2 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G16 (55.1 mg of colorless solid, yield 75%).

[0109] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.69 (m, 1H), 8.60–8.57 (m, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.83 (d, J = 8.3 Hz, 1H), 7.70 (dd, J = 8.3, 1.8 Hz, 1H), 7.61 (s, 1H), 7.50–7.45 (m, 2H), 7.40 (dd, J = 8.4, 1.7 Hz, 1H), 7.35 (d, J = 7.9 Hz, 2H), 2.96 (q, J = 7.6 Hz, 2H), 2.79 (q, J = 7.6 Hz, 2H), 1.54 (s, 9H), 1.42 (t, J = 7.6 Hz, 3H), 1.36 (t, J = 7.6 Hz, 3H).13 13C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 143.3, 142.4, 138.5, 138.1, 131.0, 130.1, 129.8, 129.7, 129.4, 128.4, 127.9, 127.2, 126.9, 126.4, 125.2, 121.4, 118.2, 35.4, 31.7, 29.6, 28.8, 16.3, 15.8. IR (ATR): ν 3019, 2959, 2870, 1781, 1602, 1509, 1461, 1364, 1287, 1200, 1058, 834, 734 cm 1 . HRMS (APCI, m / z): calcd for C 28 H 30 + (M) + : 366.2342; found: 366.2335.

[0110] Example 23:

[0111]

[0112] To a dry photoreaction tube equipped with a magnetic stir bar was added A (106.4 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G1 (58.8 mg of colorless solid, yield 74%).

[0113] 11H NMR (600 MHz, CDCl3, 25 °C) δ 8.74 (d, J = 1.8 Hz, 1H), 8.62 (d, J = 1.8 Hz, 1H), 7.94 (d, J = 8.5 Hz, 1H), 7.84 (d, J = 8.3 Hz, 1H), 7.70 (dd, J = 8.3, 1.8 Hz, 1H), 7.62 (s, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.47–7.45 (m, 1H), 7.39 (d, J = 8.1 Hz, 2H), 3.25 (hept, J = 6.9 Hz, 1H), 3.05 (hept, J = 6.9 Hz, 1H), 1.55 (s, 9H), 1.45 (d, J = 6.9 Hz, 6H), 1.38 (d, J = 6.9 Hz, 6H). 13 13C NMR (151 MHz, CDCl3, 25 °C) δ 149.1, 147.9, 146.8, 138.6, 138.1, 130.9, 130.1, 129.9, 129.9 129.5, 128.4, 127.3, 126.4, 126.4, 125.2, 125.1, 120.1, 118.1, 35.4, 34.8, 34.1, 31.7, 24.4, 24.3. IR (ATR): ν 3019, 2959, 2870, 1781, 1602, 1509, 1412, 1364, 1267, 1203, 1051, 838, 734 cm 1 . HRMS (APCI, m / z): calcd for C 30 H 34 + (M) + : 394.2655; found: 394.2652.

[0114] Example 24:

[0115]

[0116] To a dry photoreaction tube equipped with a magnetic stir bar was added A (140 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the lamp was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G18 (57.7 mg of colorless solid, yield 61%).

[0117] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.72 (d, J = 2.2 Hz, 1H), 8.57 (s, 1H), 7.89 (dd, J = 8.4, 2.7 Hz, 1H), 7.84 (dd, J = 8.5, 2.0 Hz, 1H), 7.70 (dd, J = 8.3, 2.0 Hz, 1H), 7.61 (d, J = 2.5 Hz, 1H), 7.48–7.46 (m, 2H), 7.39 (d, J = 8.5 Hz, 1H), 7.35–7.32 (m, 2H), 2.92 (t, J = 7.6 Hz, 2H), 2.74 (t, J = 7.7 Hz, 2H), 1.82–1.77 (m, 2H), 1.76–1.71 (m, 2H), 1.48–1.43 (m, 4H), 1.40–1.35 (m, 8H), 0.97–0.92 (m, 6H). 13 13C NMR (151 MHz, CDCl3, 25 °C) δ 149.1, 142.0, 141.0, 138.5, 138.1, 130.9, 130.1, 129.9, 129.7, 129.4, 128.4, 128.4, 127.3, 127.1, 126.3, 125.1, 122.0, 118.2, 36.6, 36.0, 35.4, 32.0, 32.0, 31.9, 31.7, 31.7, 29.3, 29.3, 22.8, 22.8, 22.8, 14.3. IR (ATR): ν 3022, 2952, 2855, 1774, 1688, 1602, 1509, 1461, 1364, 1267, 1200, 1021, 827, 730 cm 1 . HRMS (APCI, m / z): calcd for C 36 H 47 + (M + H) + : 479.3672; found: 479.3660.

[0118] Example 25:

[0119]

[0120] To a dry photoreaction tube equipped with a magnetic stir bar, add A (117.6 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 hours. Then turn off the lamp and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to obtain the target compound G19 (49.1 mg of colorless solid, yield 58%).

[0121] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.76 (d, J = 2.0 Hz, 1H), 8.70 (d, J = 1.8 Hz, 1H), 7.91 (d, J = 8.7 Hz, 1H), 7.81 (d, J = 8.4 Hz, 1H), 7.68 (dd, J = 8.3, 1.8 Hz, 1H), 7.62–7.59 (m, 2H), 7.52 (d, J = 8.3 Hz, 2H), 7.49–7.46 (m, 2H), 1.52 (s, 9H), 1.51 (s, 9H), 1.42 (s, 9H). 13 C NMR (151 MHz, CDCl3, 25 °C) δ 150.2, 149.1, 148.9, 138.2, 137.9, 130.5, 129.9, 129.8, 129.7, 129.4, 128.5, 126.9, 126.5, 125.3, 125.1, 124.6, 118.3, 117.9, 35.4, 35.2, 34.8, 31.7, 31.6. IR (ATR): ν 3056, 2959, 2866, 1744, 1602, 1517, 1464, 1364, 1267, 1200, 1021, 838, 738 cm 1 . HRMS (APCI, m / z): calcd for C 32 H 38 + (M) + : 422.2968; found: 422.2968.

[0122] Example 26:

[0123]

[0124] To a dry photoreaction tube equipped with a magnetic stir bar, add A (96.8 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 h. Then turn off the lamp and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G20 (50.5 mg of colorless solid, yield 68%).

[0125] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.62–8.58 (m, 1H), 8.18 (d, J = 2.6 Hz, 1H), 7.87 (d, J = 9.0 Hz, 1H), 7.82 (d, J = 8.3 Hz, 1H), 7.69 (dd, J = 8.3, 1.8 Hz, 1H), 7.51 (s, 1H), 7.49–7.43 (m, 2H), 7.18 (dd, J = 9.0, 2.6 Hz, 1H), 7.05 (d, J = 8.6 Hz, 2H), 4.05 (s, 3H), 3.91 (s, 3H), 1.52 (s, 9H). 13 13C NMR (151 MHz, CDCl3, 25 °C) δ 159.0, 158.1, 149.0, 137.7, 133.6, 132.4, 131.2, 130.2, 129.0, 128.7, 128.4, 126.3, 125.5, 125.0, 118.2, 115.4, 113.8, 105.0, 55.7, 55.5, 35.3, 31.7. IR (ATR): ν 3134, 2996, 2862, 2838, 1774, 1613, 1572, 1520, 1461, 1364, 1285, 1244, 1036, 831, 738 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 O2 + (M + H) + : 371.2006; found: 371.2001.

[0126] Example 27:

[0127]

[0128] To a dry photoreaction tube equipped with a magnetic stir bar, add A (117.8 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 h. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to obtain the target compound G21 (51.7 mg of colorless solid, yield 61%).

[0129] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.72–8.68 (m, 1H), 8.53–8.52 (m, 1H), 7.87 (d, J = 8.4 Hz, 1H), 7.83 (d, J = 8.3 Hz, 1H), 7.70 (dd, J = 8.3, 1.8 Hz, 1H), 7.62 (s, 1H), 7.48–7.45 (m, 2H), 7.35 (dd, J = 8.4, 1.6 Hz, 1H), 7.31–7.28 (m, 2H), 2.78 (d, J = 7.3 Hz, 2H), 2.60 (d, J = 7.2 Hz, 2H), 2.06 (dp, J = 13.6, 6.8 Hz, 1H), 1.98 (dp, J = 13.6, 6.8 Hz, 1H), 1.54 (s, 9H), 1.01 (d, J = 6.6 Hz, 12H). 13 C NMR (151 MHz, CDCl3, 25 °C) δ 149.1, 140.8, 139.8, 138.5, 138.2, 130.8, 129.9, 129.8, 129.7, 129.4, 129.1, 128.4, 127.9, 126.9, 126.3, 125.1, 122.7, 118.1, 46.0, 45.4, 35.4, 31.7, 30.6, 30.5, 22.7. IR (ATR): ν 3019, 2922, 2862, 1744, 1606, 1509, 1461, 1382, 1274, 1203, 1021, 842, 752 cm 1 . HRMS (APCI, m / z): calcd for C 32 H 38 + (M) + : 422.2968; found: 422.2960.

[0130] Example 28:

[0131]

[0132] To a dry photoreaction tube equipped with a magnetic stir bar, add A (84.8 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube, then irradiate with a 6 W 365 nm LED lamp, and stir the reaction mixture at room temperature for 12 h. Then turn off the lamp and concentrate the reaction mixture under reduced pressure. Purify the crude product by silica gel column chromatography (200 - 300 mesh) and elute with PE / EA (100 / 1 - 50 / 1, v / v) to obtain the target compound G22 (52.2 mg of colorless solid, yield 76%).

[0133] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.61–8.60 (m, 1H), 8.18 (d, J = 2.6 Hz, 1H), 7.84 (dd, J = 10.9, 8.7 Hz, 2H), 7.70 (dd, J = 8.3, 1.9 Hz, 1H), 7.55–7.49 (m, 5H), 7.47–7.43 (m, 1H), 7.18 (dd, J = 9.0, 2.6 Hz, 1H), 4.05 (s, 3H), 1.52 (s, 9H). 13 C NMR (151 MHz, CDCl3, 25 °C) δ 158.2, 149.1, 141.2, 138.1, 132.4, 130.2, 130.1, 129.1, 128.7, 128.5, 128.4, 127.4, 126.1, 125.5, 125.0, 118.2, 115.5, 105.0, 55.7, 35.4, 31.7. IR (ATR): ν 3019, 2959, 2866, 1751, 1648, 1617, 1569, 1520, 1416, 1289, 1230, 1039, 820, 738 cm 1 . HRMS (APCI, m / z): calcd for C 25 H 25 O + (M + H) + : 341.1900; found: 341.1898.

[0134] Example 29:

[0135]

[0136] To a dry photoreaction tube equipped with a magnetic stir bar, add A (147.6 mg, 0.6 mmol, 3 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 h. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G23 (54.0 mg of colorless solid, yield 72%).

[0137] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.61–8.59 (m, 1H), 8.17 (d, J = 2.6 Hz, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.78 (d, J = 9.0 Hz, 1H), 7.70 (dd, J = 8.4, 1.8 Hz, 1H), 7.49 (s, 1H), 7.48–7.44 (m, 4H), 7.18 (dd, J = 9.0, 2.6 Hz, 1H), 4.05 (s, 3H), 1.51 (s, 9H). 13 C NMR (151 MHz, CDCl3, 25 °C) δ 158.3, 149.4, 139.7, 136.8, 133.3, 132.4, 131.5, 129.9, 129.2, 128.6, 128.5, 128.3, 125.8, 125.6, 125.1, 118.3, 115.6, 105.1, 55.7, 35.4, 31.7. IR (ATR): ν 3049, 2963, 2870, 1770, 1617, 1520, 1490, 1416, 1364, 1289, 1230, 1039, 827, 738 cm 1 . HRMS (APCI, m / z): calcd for C 25 H 23 ClO + (M) + : 374.1432; found: 374.1432.

[0138] Example 30:

[0139]

[0140] To a dry photoreaction tube equipped with a magnetic stir bar, add A (168 mg, 0.6 mmol, 3 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 h. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G24 (64.2 mg of colorless solid, yield 75%).

[0141] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.62–8.60 (m, 1H), 8.19 (d, J = 2.6 Hz, 1H), 7.83 (d, J = 8.3 Hz, 1H), 7.76 (dd, J = 9.7, 8.4 Hz, 3H), 7.72 (dd, J = 8.4, 1.8 Hz, 1H), 7.65–7.63 (m, 2H), 7.51 (s, 1H), 7.19 (dd, J = 9.0, 2.5 Hz, 1H), 4.06 (s, 3H), 1.52 (s, 9H). 13 C NMR (151 MHz, CDCl3, 25 °C) δ 158.2, 149.5, 144.9, 136.5, 132.4, 130.4, 129.7, 129.4 (q, J = 32.6 Hz), 129.2, 128.5, 128.1, 125.6, 125.4, 125.3 (q, J = 3.0 Hz), 125.2, 124.4 (q, J = 273.3 Hz), 118.2, 115.7, 105.0, 55.6, 35.3, 31.6. IR (ATR): ν 3090, 2963, 2870, 1744, 1617, 1513, 1464, 1416, 1326, 1230, 1125, 1039, 849, 738 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 23 F3O + (M) + : 408.1696; found: 408.1693.

[0142] Example 31:

[0143]

[0144] To a dry photoreaction tube equipped with a magnetic stir bar was added A (168 mg, 0.6 mmol, 3 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). The photoreaction tube was sealed and then irradiated with a 6 W 365 nm LED lamp. The reaction mixture was stirred at room temperature for 12 h. Then the light was turned off and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G25 (64.2 mg of colorless solid, yield 75%).

[0145] R f = 0.42 (PE). mp: 89.9 - 92.0 °C. NMR Spectroscopy [mixture of rotamers]: 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.67–8.66 (m, 1H, H), 8.53 (s, 1H, H’), 7.81 (dd, J = 12.9, 8.3 Hz, 1H, H + H’), 7.71–7.64 (m, 2H, H + H’), 7.54 (d, J = 13.2 Hz, 1H, H + H’), 7.34–7.32 (m, 1H, H + H’), 7.29–7.28 (m, 1H, H + H’), 7.27–7.24 (m, 1H, H + H’), 3.01 (s, 1H, H’), 2.57 (d, J = 2.7 Hz, 3H, H + H’), 2.40–2.35 (m, 8H, H + H’), 1.51 (s, J = 18.7 Hz, 9H, H + H’). 1313C NMR (151 MHz, CDCl3, 25 °C) δ 149.0, 147.2 (C’), 139.0 (C’), 139.0, 138.4 (C’), 137.8, 136.6, 136.5 (C’), 136.3 (C’), 135.6, 135.6, 135.5 (C’), 133.1, 131.8 (C’), 131.5 (C’), 131.4, 131.3 (C’), 131.1, 130.1 (C’), 130.0, 129.6, 129.6 (C’), 129.5, 129.3 (C’), 129.2, 128.3 (C’), 128.3, 127.9 (C’), 127.7 (C’), 127.6 (C’), 127.2, 126.4 (C’), 126.3, 124.9 (C’), 124.7, 124.5 (C’), 124.2, 123.1 (C’), 118.0 (C + C’), 35.4, 35.3 (C’), 31.7 (C + C’), 22.3, 21.7 (C’), 20.6, 20.3 (C’), 20.1, 20.0 (C’), 19.8, 19.7 (C’). IR (ATR): ν 3019, 2959, 2866, 1774, 1688, 1602, 1502, 1449, 1364, 1267, 1207, 1021, 827, 734 cm 1 . HRMS (APCI, m / z): calcd for C 28 H 31 + (M + H) + : 367.2420; found: 367.2412.

[0146] Example 32:

[0147]

[0148] Add A (84 mg, 0.4 mmol, 2 equiv.), B (34 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL) to a dry photoreaction tube equipped with a magnetic stir bar. Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. Stir the reaction mixture at room temperature for 12 hours. Then turn off the light and concentrate the reaction mixture under reduced pressure. Purify the crude product by silica gel column chromatography (200 - 300 mesh) and elute with PE / EA (100 / 1 - 50 / 1, v / v) to obtain the target compound G26 (51.8 mg of colorless solid, yield 83%).

[0149] Rf = 0.40 (PE / EA = 50 / 1 (v / v)). mp: 104.1 - 106.3 °C. NMR Spectroscopy: 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.61 (d, J = 9.0 Hz, 1H), 8.47–8.45 (m, 1H), 7.80 (d, J = 8.3 Hz, 1H), 7.54 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 7.8 Hz, 2H), 7.30 (dd, J = 8.4, 1.6 Hz, 1H), 7.27 (dd, J = 9.1, 2.7 Hz, 1H), 7.24 (d, J = 2.7 Hz, 1H), 3.96 (s, 3H), 2.61 (s, 3H), 2.48 (s, 3H). 13 13C NMR (151 MHz, CDCl3, 25 °C) δ 158.5, 139.4, 138.2, 137.1, 136.3, 133.3, 131.0, 130.0, 129.1, 128.2, 127.3, 127.0, 126.2, 124.3, 124.1, 122.3, 117.0, 108.5, 55.5, 22.1, 21.4. IR (ATR): ν 3067, 2944, 2832, 1774, 1617, 1498, 1446, 1431, 1364, 1244, 1174, 1043, 827, 730 cm 1 . HRMS (APCI, m / z): calcd for C 23 H 21 O + (M + H) + : 313.1587; found: 313.1581.

[0150] Example 33:

[0151]

[0152] To a dry photoreaction tube equipped with a magnetic stir bar, add A (84 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), 2,4,6-collidine (24.2 mg, 0.2 mmol, 1 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 hours. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to obtain the target compound G1 (45.2 mg of colorless solid, yield 72%).

[0153] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 13 C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 .HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0154] Example 34:

[0155]

[0156] Add A (84 mg, 0.4 mmol, 2 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL) to a dry photoreaction tube equipped with a magnetic stir bar. Seal the photoreaction tube and then irradiate it with a 6 W 460 nm LED lamp. The reaction mixture is stirred at room temperature for 12 h. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G1 (5.4 mg of colorless solid, yield 12%).

[0157] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 13 C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0158] Example 35:

[0159]

[0160] To a dry photoreaction tube equipped with a magnetic stir bar, add A (42 mg, 0.2 mmol, 1 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 hours. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to obtain the target compound G1 (40.3 mg of colorless solid, yield 63%).

[0161] 1 1H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 13 13C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0162] Example 36:

[0163]

[0164] To a dry photoreaction tube equipped with a magnetic stir bar, add A (168 mg, 0.8 mmol, 4 equiv.), B (39.2 mg, 0.2 mmol), collidine (48.4 mg, 0.4 mmol, 2 equiv.) and dry DCM (2 mL). Seal the photoreaction tube and then irradiate it with a 6 W 365 nm LED lamp. The reaction mixture is stirred at room temperature for 12 h. Then turn off the light and concentrate the reaction mixture under reduced pressure. The crude product is purified by silica gel column chromatography (200 - 300 mesh) and eluted with PE / EA (100 / 1 - 50 / 1, v / v) to give the target compound G1 (54.7 mg of colorless solid, yield 81%).

[0165] 1 H NMR (600 MHz, CDCl3, 25 °C) δ 8.74–8.65 (m, 1H), 8.61–8.54 (m, 1H), 7.82 (dd, J = 8.3, 4.9 Hz, 2H), 7.69 (dd, J = 8.3, 1.9 Hz, 1H), 7.58 (s, 1H), 7.45–7.42 (m, 2H), 7.35 (dd, J = 8.4, 1.7 Hz, 1H), 7.34–7.30 (m, 2H), 2.65 (s, 3H), 2.48 (s, 3H), 1.53 (s, 9H). 13 C NMR (151 MHz, CDCl3, 25 °C) δ 149.2, 138.3, 138.1, 137.0, 136.0, 131.0, 130.1, 129.8, 129.4, 129.3, 129.1, 128.4, 128.1, 127.0, 126.3, 125.2, 122.6, 118.2, 35.4, 31.7, 22.1, 21.4. IR (ATR): ν 3019, 2918, 2858, 1736, 1617, 1505, 1435, 1317, 1244, 1218, 1036, 820, 730 cm 1 . HRMS (APCI, m / z): calcd for C 26 H 27 + (M + H) + : 339.2107; found: 339.2103.

[0166] The above are the preferred embodiments of the present invention. Of course, the scope of the rights of the present invention cannot be limited thereby. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and changes can be made, and these improvements and changes are also regarded as the protection scope of the present invention.

Claims

1. A method for synthesizing a phenanthrene compound, characterized in that: Mix diaryl ketone A, difluoroolefin B, an additive and an organic solvent, stir and react the mixed solution under the conditions of light and 0 - 30 °C, and then separate and purify to obtain the phenanthrene compound; The molecular structural formula of the phenanthrene compound is shown as follows: ； The molecular structural formula of the diaryl ketone A is ; The molecular structural formula of the difluoroolefin B is as follows: ; wherein R1, R2, R3, R4, R5, and R6 are each any one of aryl, alkyl, alkoxy, and hydrogen atom; The alkyl has 1 - 20 carbon atoms and is a straight-chain structure or a branched-chain structure; The organic solvent is at least one of methanol, ethanol, isopropanol, tert-butanol, tetrahydrophenanthrene, 2-methyltetrahydrophenanthrene, diethyl ether, dimethyldiethylether, methyl tert-butyl ether, 1,4-epoxyhexane, 1,3-epoxyhexane, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, C 4-12 saturated alkanes, C 3-12 fluorinated or chlorinated alkanes, dimethyl sulfoxide, N , N -dimethylformamide, N , N -dimethylacetamide, acetone, N -methylpyrrolidone, acetonitrile, C 3-12 saturated alkyl nitriles; The additive is at least one of 2,4,6-collidine, 2,6-lutidine, pyridine, triethylamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), and 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), and the molar ratio of the additive to difluoroolefin B is 1 - 3:

1.

2. The synthesis method of the phenanthrene compound according to claim 1, wherein: The molar ratio between diaryl ketone A and difluoroolefin B is 1 - 4:1; the concentration of difluoroolefin B in the mixed solution is between 0.1 M and 1 M.

3. The synthesis method of the phenanthrene compound according to claim 1, characterized in that: The light source of the light is any one of visible light and ultraviolet light.

4. The synthesis method of the phenanthrene compound according to claim 1, characterized in that: The separation and purification include filtration, concentration, recrystallization, and column chromatography.

5. A method for synthesizing a phenanthrene compound, characterized in that: Add 84 mg of A, 39.6 mg of B, 48.4 mg of 2,4,6-collidine and 2 mL of dry dichloromethane into a dry photoreaction tube equipped with a magnetic stirrer, seal the photoreaction tube, then irradiate it with a 6 W 365 nm LED lamp, stir the reaction mixture at room temperature for 12 hours, then turn off the light, concentrate the reaction mixture under reduced pressure, purify the product by silica gel column chromatography with 200 - 300 mesh, and elute with petroleum ether / ethyl acetate with a volume ratio of 100 / 1 - 50 / 1 to obtain the phenanthrene compound. The reaction formula is shown as follows, wherein the phenanthrene compound is shown as G7 in the reaction formula: 。

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