Synthesis method for constructing new C-C bond and C-X bond under catalysis of oriental organic photo-oxidation reduction catalyst and application of novel C-C bond and C-X bond

Abstract

The invention relates to a synthesis method and application of a new C-C bond and a C-X (X = heteroatom) bond under the catalysis of an organic photo-oxidation reduction catalyst, the synthesis method avoids the use of aryl halides, and reduces environmental pollution; in addition, aryl sulfosalt is used as an electrophilic reagent in the reaction, so that the site selectivity of the reaction is improved; the use of an organic metal reagent is avoided in the reaction, and the toxicity and instability of the organic metal reagent are avoided. The use of a noble metal catalyst is avoided, and the cost of organic synthesis of the compound is reduced by using cheap Zongxiang as an organic photooxidation reduction catalyst; the reaction avoids the use of an organic photooxidation reduction catalyst which contains auxochrome groups and is unstable in structure, and the stability of the photocatalyst is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of constructing new CC bonds and CX bonds, in particular to a synthesis method and application of constructing new CC bonds and CX (X=heteroatom) bonds by catalyzing a rubicine organic photoredox catalyst. Background Art

[0002] Aryl trifluoromethyl compounds, biaryl fragments (Ar1-Ar2), heteroaryl compounds and heteroalkyl compounds are among the most important functional groups in medicines, pesticides and organic functional materials. Therefore, the synthesis of new CC bonds and CX (X = heteroatom) bonds through catalytic cross-coupling reactions has always been a research hotspot.

[0003] Aryl trifluoromethyl compounds, biaryl fragments (Ar1-Ar2), heteroaryl compounds and heteroalkyl compounds are generally synthesized by cross-coupling reactions of organic halides and organometallic reagents catalyzed by noble metals. However, organometallic reagents have the disadvantages of high toxicity and instability, high price of noble metal catalysts, toxicity of organic halides, and structurally unstable auxochromophores contained in widely used organic photoredox catalysts. Therefore, the development of non-toxic, environmentally friendly, highly selective and low-cost methods for synthesizing aryl trifluoromethyl compounds, biaryl fragments (Ar1-Ar2), heteroaryl compounds and heteroalkyl compounds using structurally stable photocatalysts has always been a hot topic for scientists.

[0004] Recently, scientists have used highly site-selective organic sulfonium salts instead of organic halides as electrophilic reagents to achieve the construction of aryl trifluoromethyl compounds, biaryl fragments (Ar1-Ar2), heteroaryl compounds and heteroalkyl compounds, but scientists still use precious metals as catalysts. Photoredox catalytic reactions have the characteristics of mild conditions, green environmental protection, and few side reactions. Currently, a widely used type of photoredox catalyst is a precious metal photoredox catalyst based on ruthenium, iridium and osmium. This type of catalyst has the disadvantages of high price and residual catalyst damage to human organs during drug synthesis; another type of photoredox catalyst is metal-free organic photoredox catalyst, such as eosin Y, acridine, methylene blue and benzophenone. In order to make the catalyst absorb visible light, this type of photoredox catalyst usually introduces unstable carboxyl, amino, ketocarbonyl, halogen and amide auxochromophores.

[0005] As a type of organic photoredox catalyst, hong (a fully conjugated rigid structure that can reach the visible light absorption range without the introduction of auxochromes) has the advantages of low price, no auxochromes, stable structure, and simple separation and purification during drug synthesis. The use of hong as a photoredox catalyst to catalyze organic synthesis reactions has not been reported before, so the use of hong as an organic photoredox catalyst to catalyze organic synthesis reactions has potential advantages and important significance.

[0006] Through searching, no patent publication documents related to the patent application of the present invention were found. Summary of the invention

[0007] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a synthesis method and application of new CC bonds and CX bonds catalyzed by organic photoredox catalysts, which effectively avoids the use of aryl halides and reduces environmental pollution.

[0008] The present invention solves the technical problem by adopting the following technical solutions:

[0009] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, comprising any of the following methods:

[0010] Method 1: Using aryl sulfide and [CuCF3] as reaction materials, trifluoromethylation of aryl sulfide is achieved under catalyst, solvent and light conditions; wherein the catalyst is S-rubicene, acetone is used as solvent, and 40 watt blue light LED is used to irradiate the aryl sulfide at room temperature to achieve trifluoromethylation;

[0011] Or method 2: using an aryl sulfide salt and a heteroaromatic ring compound as reaction raw materials, achieving heteroarylation of the aryl sulfide salt under the conditions of a catalyst, a base, a solvent, and light; wherein the catalyst is S-rubicene, the base is potassium acetate, dimethyl sulfoxide is used as the solvent, and the aryl sulfide salt is irradiated with a 40-watt blue light LED at room temperature to achieve heteroarylation;

[0012] Or method 3: using aryl sulfide and biboric acid pinacol ester as reaction raw materials, borate esterification of aryl sulfide is achieved under the conditions of catalyst, organic base, solvent and light; wherein the catalyst is rubicene, the organic base is pyridine, acetone is used as solvent, and 40 watt blue light LED is used to irradiate the aryl sulfide at room temperature;

[0013] Or method 4: using an aryl sulfide and a disulfide as the reaction raw materials, and realizing the thioetherification of the aryl sulfide under the conditions of a catalyst / organic base, a solvent, and light; wherein the catalyst is S-rubicene, the organic base is pyridine, acetone is used as the solvent, and the thioetherification of the aryl sulfide is realized under room temperature conditions by irradiation with a 40-watt blue light LED;

[0014] Or method 5: using aromatic vinyl and disulfide as reaction raw materials, realizing the thioetherification of aromatic vinyl under the conditions of catalyst, organic base, solvent and light; wherein the catalyst is Se-rubicene, the organic base is 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester, using acetonitrile as solvent, realizing the thioetherification of aromatic vinyl under room temperature conditions by irradiation with a 40-watt blue light LED.

[0015] Moreover, the reaction formulas of method 1, method 2, method 3, method 4 and method 5 are respectively as follows:

[0016]

[0017]

[0018] Wherein, X is a heteroatom, including but not limited to O, S, Se, and N; Method 3:

[0019]

[0020]

[0021] Wherein, Ar1 represents different aromatic systems; X represents a heteroatom, including but not limited to O, S, Se, Te, and N; and R represents different aromatic, heteroaromatic or alkyl systems.

[0022] Moreover, the structural formula of Hong is shown below:

[0023]

[0024] Moreover, the aryl sulfide salt is any one of the following compounds:

[0025]

[0026]

[0027] The aromatic vinyl is any one of the following compounds:

[0028]

[0029] Wherein, R, R1, and R2 are independent C1-C15 alkyl chains, and the C1-C15 alkyl chains include straight-chain alkyl groups with a total number of carbon atoms of 1 to 15, branched-chain alkyl groups with a total number of carbon atoms of 3 to 15, or cycloalkyl groups with a total number of carbon atoms of 3 to 8.

[0030] Furthermore, the straight-chain alkyl group having a total carbon atom count of 1 to 15 includes: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n-pentadecyl;

[0031] The branched alkyl group having a total of 3 to 15 carbon atoms includes isopropyl, tert-butyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl and 3-ethyltridecyl;

[0032] The cycloalkyl group having 3 to 8 carbon atoms includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0033] Furthermore, the heteroaromatic compound is any one of the following compounds:

[0034]

[0035] Moreover, the disulfide is any one of the following compounds:

[0036]

[0037] Wherein, R is an independent C1-C15 alkyl chain, and the C1-C15 alkyl chain includes a straight chain alkyl group with a total carbon atom number of 1-15, a branched chain alkyl group with a total carbon atom number of 3-15, or a cycloalkyl group with a total carbon atom number of 3-8.

[0038] Moreover, the method 1, method 2, method 3, method 4 and method 5 include the following steps:

[0039] Method 1:

[0040] (1) Using inert gas protection, under the catalytic action of S-rubicene, aryl sulfide salt and [CuCF3] are placed in acetone, and reacted at room temperature under the irradiation of blue light LED to obtain a mixture;

[0041] (2) adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter;

[0042] Method 2:

[0043] (1) using inert gas protection, under the catalytic action of S-rubicene, adding potassium acetate as an additive, placing an aryl sulfide salt and a heteroaromatic ring compound in dimethyl sulfoxide, reacting at room temperature under the irradiation of a blue light LED to obtain a mixture;

[0044] (2) adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter;

[0045] Method 3:

[0046] (1) using inert gas protection, under the catalytic action of rubicene, adding pyridine as an additive, placing aryl sulfide salt and biboric acid pinacol ester in acetone, reacting at room temperature under the irradiation of blue light LED to obtain a mixture;

[0047] (2) adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter;

[0048] Method 4:

[0049] (1) Using inert gas protection, under the catalytic action of S-rubicene, adding pyridine as an additive, placing the aryl sulfide and the disulfide in acetone, reacting at room temperature under the irradiation of a blue LED to obtain a mixture;

[0050] (2) adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter;

[0051] Method 5:

[0052] (1) Under inert gas protection, under the catalytic action of Se-rubicene, 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester is added as an additive, aromatic vinyl and disulfide are placed in acetonitrile, and reacted at room temperature under the irradiation of blue LED to obtain a mixture;

[0053] (2) Adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter.

[0054] Moreover, the method 1, method 2, method 3, method 4 and method 5 specifically include the following steps:

[0055] Method 1: 1.0 equivalent of aryl sulfide salt, 1.5 equivalent of [CuCF3], and S-rubicene are placed in a reaction bottle, and the amount of S-rubicene added is 1.0 mol% of the total molar amount of aryl sulfide salt; after replacing nitrogen three times, dry acetone is added to keep the concentration of the solution at 0.025 M; after stirring for 12 hours at room temperature under 40-watt blue light LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained by rapid column chromatography;

[0056] Method 2: 1.0 equivalent of aryl sulfide, 5.0 equivalent of potassium acetate and S-rubicene are placed in a reaction bottle, and the amount of S-rubicene added is 1.0 mol% of the total molar amount of aryl sulfide; after replacing nitrogen three times, 20.0 equivalents of heteroaromatic hydrocarbons are added; dry dimethyl sulfoxide is added to keep the concentration of the solution at 0.2 M; after stirring for 35 hours at room temperature under 40-watt blue LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained by rapid column chromatography;

[0057] Method 3: 1.0 equivalent of aryl sulfide salt, 5.0 equivalent of biboric acid pinacol ester and rubicene are placed in a reaction bottle, and the amount of rubicene added is 2.0 mol% of the total molar amount of aryl sulfide salt; after replacing nitrogen three times, 5.0 equivalent of pyridine is added; dry acetone is added to keep the concentration of the solution at 0.25M; after stirring for 35 hours at room temperature under 40-watt blue light LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained by rapid column chromatography;

[0058] Method 4: 1.0 equivalent of aryl sulfide, 5.0 equivalent of disulfide and S-rubicene are placed in a reaction bottle, and the amount of S-rubicene added is 2.0 mol% of the total molar amount of aryl sulfide; after replacing nitrogen three times, 5.0 equivalent of pyridine is added; dry acetone is added to keep the concentration of the solution at 0.5 M; after stirring for 35 hours at room temperature under 40-watt blue LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained by rapid column chromatography;

[0059] Method 5: 5.0 equivalents of disulfide, 2.0 equivalents of di-tert-butyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate and Se-rubicene are placed in a reaction bottle, and the amount of Se-rubicene added is 1.0 mol% of the total molar amount of aromatic vinyl; after replacing nitrogen three times, 1.0 equivalent of aromatic vinyl is added; dry acetonitrile is added to keep the concentration of the solution at 0.1 M; after stirring for 28 hours at room temperature under 40-watt blue light LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained through a rapid column machine.

[0060] A synthetic method for constructing new CC bonds and CX bonds using an organic photoredox catalyst is used in the post-modification of drugs.

[0061] The advantages and positive effects of the present invention are:

[0062] 1. The synthesis method of the present invention avoids the use of aryl halides, thereby reducing environmental pollution; in addition, the reaction uses aryl sulfide salts as electrophilic reagents, thereby improving the site selectivity of the reaction; the reaction avoids the use of organometallic reagents, thereby avoiding the toxicity and instability of organometallic reagents.

[0063] 2. The synthesis method of the present invention avoids the use of precious metal catalysts and uses cheap chlorine as an organic photoredox catalyst, thereby reducing the cost of organic synthetic compounds; the reaction avoids the use of organic photoredox catalysts containing auxochromophores and unstable structures, thereby improving the stability of the photocatalyst.

[0064] 3. The method of the present invention can be applied to the post-modification of drugs. DETAILED DESCRIPTION

[0065] The present invention is further described in detail below through specific examples. The following examples are only illustrative and not restrictive, and the protection scope of the present invention cannot be limited thereto.

[0066] The various experimental operations involved in the specific embodiments are all routine techniques in the art. For parts not specially annotated in this document, ordinary technicians in the art can implement them by referring to various commonly used reference books, scientific and technological literature or related instructions, manuals, etc. before the filing date of this invention.

[0067] Example 1

[0068] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 1:

[0069]

[0070] 1.0 equivalent of biphenyl-derived dibenzothiophene sulfonate (0.2mmol, 97.3mg) and S-rubicene (0.002mmol, 1.8mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.5 equivalent of [CuCF3] (0.3mmol, 1.0mL) and dry acetone (8.0mL) were added. After irradiation with a 40-watt blue LED (467nm) at room temperature and stirring for 12 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless solid (38.7mg, 87%) was obtained by rapid column chromatography.

[0071] 1 H NMR (500MHz, CDCl3): δ7.72 (s, 4H), 7.63 (d, J = 7.3Hz, 2H), 7.50 (t, J = 7.5Hz, 2H), 7.44 (t, J = 7.3Hz, 1H). 13 C NMR (126MHz, CDCl3): δ144.70, 139.73, 129.31 (q, J = 32.5Hz), 128.97, 128.17, 127.39, 127.26, 125.69 (q, J = 3.6Hz), 124.31 (q, J = 271.9Hz). 19 F NMR (471MHz, CDCl3): δ-62.25.

[0072] Example 2

[0073] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 1:

[0074]

[0075] 1.0 equivalent of bromobenzene-derived dibenzothiophene sulfonate (0.2mmol, 97.9mg) and S-rubicene (0.002mmol, 1.9mg) were placed in a reaction flask. After replacing nitrogen three times, 1.5 equivalent of [CuCF3] (0.3mmol, 1.0mL) and dry acetone (8.0mL) were added. After irradiation with a 40-watt blue LED (467nm) at room temperature and stirring for 12 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A colorless oily liquid (32.4mg, 72%) was obtained by rapid column chromatography.

[0076] 1 H NMR (500MHz, CDCl3): δ7.61 (d, J = 8.2 Hz, 2H), 7.49 (d, J = 8.2 Hz, 2H).13 C NMR (126MHz, CDCl3): δ 132.04, 129.55 (q, J = 33.0Hz), 126.83 (q, J = 3.0Hz), 126.44, 123.89 (q, J = 272.0Hz). 19 F NMR (471MHz, CDCl3): δ-62.98.

[0077] Example 3

[0078] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 1:

[0079]

[0080] 1.0 equivalent of ethyl benzoate-derived dibenzothiophene sulfonate (0.2mmol, 96.5mg) and S-rubicene (0.002mmol, 1.8mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.5 equivalents of [CuCF3] (0.3mmol, 1.0mL) and dry acetone (8.0mL) were added. After irradiation with a 40-watt blue LED (467nm) at room temperature and stirring for 12 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (31.9mg, 73%) was obtained by rapid column chromatography.

[0081] 1 H NMR (500MHz, CDCl3): δ8.28 (s, 1H), 8.20 (d, J = 7.9Hz, 1H), 7.76 (d, J = 7.8Hz, 1H), 7.53 (t, J = 7.8Hz, 1H), 4.39 (q, J = 7.1Hz, 2H), 1.39 (t, J = 7.1Hz, 3H). 13 C NMR (126MHz, CDCl3): δ165.14, 132.67, 131.29, 130.89 (q, J = 33.1Hz), 129.19 (q , J=3.2Hz), 128.90, 126.34 (q, J=3.5Hz), 123.65 (q, J=272.4Hz), 61.44, 14.09. 19 F NMR (471MHz, CDCl3): δ-62.79.

[0082] Example 4

[0083] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 1:

[0084]

[0085] 1.0 equivalent of 1,2-dichlorobenzene-derived dibenzothiophene sulfonate (0.2mmol, 95.9mg) and S-rubicene (0.002mmol, 1.7mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.5 equivalent of [CuCF3] (0.3mmol, 1.0mL) and dry acetone (8.0mL) were added. After irradiation with a 40-watt blue LED (467nm) and stirring for 12 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow liquid (32.7mg, 76%) was obtained by rapid column chromatography.

[0086] 1 H NMR (500MHz, CDCl3): δ7.72 (s, 1H), 7.58 (d, J = 8.2 Hz, 1H), 7.47 (d, J = 8.2 Hz, 1H). 13 C NMR (126MHz, CDCl3): δ 136.60, 133.44, 130.98, 130.34 (q, J = 33.7Hz), 127.57, 124.51, 122.97 (q, J = 272.6Hz). 19 F NMR (471MHz, CDCl3): δ-62.75.

[0087] Example 5

[0088] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 1:

[0089]

[0090] 1.0 equivalent of 2-methoxybenzaldehyde-derived 3,7-di-tert-butyldibenzothiophene sulfonate (0.2mmol, 116.3mg) and S-rubicene (0.002mmol, 1.8mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.5 equivalent of [CuCF3] (0.3mmol, 1.0mL) and dry acetone (8.0mL) were added. After irradiation with a 40-watt blue LED (467nm) at room temperature and stirring for 12 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (27.8mg, 68%) was obtained by rapid column chromatography.

[0091] 1H NMR (500MHz, CDCl3): δ10.46 (s, 1H), 8.09 (d, J = 2.1 Hz, 1H), 7.79 (dd, J = 8.8, 2.3 Hz, 1H), 7.09 (d, J = 8.8 Hz, 1H), 4.00 (s, 3H). 13 C NMR (126MHz, CDCl3): δ188.45, 163.64, 132.50 (q, J = 3.1Hz), 125.99 (q, J = 2. 5Hz), 124.52, 123.76 (q, J = 271.4Hz), 123.23 (q, J = 33.8Hz), 112.06, 56.08. 19 F NMR (471MHz, CDCl3): δ-61.90.

[0092] Example 6

[0093] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 1:

[0094]

[0095] 1.0 equivalent of 2-methoxybromobenzene-derived dibenzothiophene sulfonate (0.2mmol, 103.9mg) and S-rubicene (0.002mmol, 1.7mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.5 equivalents of [CuCF3] (0.3mmol, 1.0mL) and dry acetone (8.0mL) were added. After irradiation with a 40-watt blue LED (467nm) at room temperature and stirring for 12 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (38.8mg, 76%) was obtained by rapid column chromatography.

[0096] 1 H NMR (500MHz, CDCl3): δ7.79 (d, J = 1.7 Hz, 1H), 7.53 (dd, J = 8.5, 1.0 Hz, 1H), 6.94 (d, J = 8.6 Hz, 1H), 3.93 (s, 3H). 13 C NMR (126MHz, CDCl3): δ158.35, 130.47, 125.91 (q, J = 3.6Hz), 123.88 (q, J = 33.5Hz), 123.47 (q, J = 271.6Hz), 111.78, 111.34, 56.36. 19 F NMR (471MHz, CDCl3): δ-61.52.

[0097] Example 7

[0098] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 1:

[0099]

[0100] 1.0 equivalent of 4-cyanoanisole-derived dibenzothiophene sulfonate (0.2mmol, 93.1mg) and S-rubicene (0.002mmol, 1.7mg) were placed in a reaction flask. After replacing nitrogen three times, 1.5 equivalents of [CuCF3] (0.3mmol, 1.0mL) and dry acetone (8.0mL) were added. After irradiation with a 40-watt blue LED (467nm) and stirring for 12 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure. A colorless oily liquid (29.4mg, 73%) was obtained by rapid column chromatography.

[0101] 1 H NMR (500MHz, CDCl3): δ7.86 (s, 1H), 7.81 (dd, J=8.7, 1.8Hz, 1H), 7.09 (d, J=8.7Hz, 1H), 3.99 (s, 3H). 13 C NMR (126MHz, CDCl3): δ160.54, 137.58, 131.28 (q, J = 5.5Hz), 122.29 (q, J = 272.9Hz), 119.95 (q, J = 32.2Hz), 117.82, 112.66, 103.79, 56.38. 19 F NMR (471MHz, CDCl3): δ-63.20.

[0102] Example 8

[0103] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0104]

[0105] 1.0 equivalent of 2-methoxybenzoic acid methyl ester-derived dibenzothiophene sulfonate (0.2mmol, 100.1mg), S-rubicene (0.002mmol, 1.9mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 326.1mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) and stirring for 12 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (33.8mg, 69%) was obtained by rapid column chromatography.

[0106] 1 H NMR (500MHz, CDCl3): δ7.83 (d, J=2.4Hz, 1H), 7.50 (dd, J=8.6, 2.3Hz, 1H), 7.02 (d, J=8 .7Hz,1H),6.70(s,1H),6.19(d,J=1.9Hz,2H),3.94(s,3H),3.90(s,3H),3.63(s,3H). 13 C NMR (126MHz, CDCl3): δ166.45,157.95,133.63,133.07,131.83,125.52,123.34,119.80,112.02,108.40,107.64,56.07,52.05,34.84.

[0107] Example 9

[0108] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0109]

[0110] 1.0 equivalent of cyclohexylbenzene-derived dibenzothiophene sulfonate (0.2mmol, 98.7mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.4mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a red solid (16.4mg, 35%) was obtained by rapid column chromatography.

[0111] 1 H NMR (500MHz, CDCl3): δ7.32(d,J=8.0Hz,2H),7.23(d,J=8.1Hz,2H),6.70(s,1H),6.19(s,2H), 3.66(s,3H),2.55-2.50(m,1H),1.92-1.85(m,4H),1.43(h,J=12.7Hz,4H),1.31-1.23(m,2H). 13 C NMR (126MHz, CDCl3): δ146.62,134.70,130.81,128.59,126.75,123.24,108.29,107.60,44.24,34.99,34.42,26.89,26.16. HRMS(EI)m / z calcd forC 17 H 21 N[M] + :239.1674, found 239.1667.

[0112] Example 10

[0113] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0114]

[0115] 1.0 equivalent of isopropylbenzene-derived dibenzothiophene sulfonate (0.2mmol, 90.8mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.4mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow liquid (17.8mg, 45%) was obtained by rapid column chromatography.

[0116] 1 H NMR (500MHz, CDCl3): δ7.34(d,J=8.1Hz,2H),7.27(d,J=2.5Hz,2H),6.71(s, 1H), 6.21 (s, 2H), 3.67 (s, 3H), 2.95 (p, J = 6.9Hz, 1H), 1.30 (d, J = 6.9Hz, 6H). 13C NMR (126MHz, CDCl3): δ147.37,134.67,130.81,128.63,126.37,123.24,108.30,107.61,34.98,33.80,23.95.

[0117] Embodiment 11

[0118] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0119]

[0120] 1.0 equivalent of 3-chloropropylbenzene-derived dibenzothiophene sulfonate (0.2mmol, 113.6mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow liquid (24.6mg, 53%) was obtained by rapid column chromatography.

[0121] 1 H NMR (500MHz, CDCl3): δ7.34(d,J=8.0Hz,2H),7.23(d,J=8.0Hz,2H),6.71(s,1H),6.20( s, 2H), 3.66 (s, 3H), 3.57 (t, J = 6.5Hz, 2H), 2.81 (t, J = 7.4Hz, 2H), 2.12 (p, J = 6.7Hz, 2H). 13 C NMR (126MHz, CDCl3): δ139.20,134.41,131.24,128.75,128.52,123.47,108.44,107.69,44.24,35.02,33.92,32.43. HRMS(EI)m / zcalcd for C 14 H 16 ClN[M] + :233.0971,found 233.0962.

[0122] Example 12

[0123] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0124]

[0125] 1.0 equivalent of iodobenzene-derived dibenzothiophene sulfonate (0.2mmol, 107.5mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a white solid (29.3mg, 52%) was obtained by rapid column chromatography.

[0126] 1 H NMR (500MHz, CDCl3): δ7.72 (d, J = 8.2 Hz, 2H), 7.14 (d, J = 8.2 Hz, 2H), 6.73 (s, 1H), 6.23 (d, J = 3.3 Hz, 1H), 6.21-6.20 (m, 1H), 3.66 (s, 3H). 13 C NMR (126MHz, CDCl3): δ137.45, 133.39, 132.77, 130.24, 124.21, 109.02, 107.99, 92.11, 35.07.

[0127] Embodiment 13

[0128] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0129]

[0130] 1.0 equivalent of 1,2-dimethoxybenzene-derived dibenzothiophene sulfonate (0.2mmol, 94.3mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a brown liquid (23.4mg, 54%) was obtained by rapid column chromatography.

[0131] 1 H NMR (500MHz, CDCl3): δ6.95-6.90(m,3H),6.70(s,1H),6.20-6.17(m,2H),3.92(s,3H),3.90(s,3H),3.64(s,3H). 13 C NMR (126MHz, CDCl3): δ148.66,148.17,134.47,126.20,123.02,121.21,112.46,111.00,108.04,107.57,55.92,55.89,34.88.

[0132] Embodiment 14

[0133] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0134]

[0135] 1.0 equivalent of 1,2-dichlorobenzene-derived dibenzothiophene sulfonate (0.2mmol, 96.3mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (28.4mg, 63%) was obtained by rapid column chromatography.

[0136] 1H NMR (500MHz, CDCl3): δ7.49 (d, J = 1.8 Hz, 1H), 7.46 (d, J = 8.3 Hz, 1H), 7.23 (dd, J = 8.3, 1. 8Hz, 1H), 6.73 (s, 1H), 6.25 (dd, J = 3.3, 1.7Hz, 1H), 6.20 (t, J = 3.0Hz, 1H), 3.67 (s, 3H). 13 C NMR (126MHz, CDCl3): δ133.30,132.40,132.01,130.64,130.27,129.99,127.56,124.63,109.64,108.14,35.10.

[0137] Embodiment 15

[0138] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0139]

[0140] 1.0 equivalent of 4-cyanoanisole-derived dibenzothiophene sulfonate (0.2mmol, 93.4mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction flask. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a purple solid (41.0mg, 97%) was obtained by rapid column chromatography.

[0141] 1 H NMR (500MHz, CDCl3): δ7.64 (dd, J=8.6, 1.7Hz, 1H), 7.56 (d, J=1.7Hz, 1H), 7.00 (d, J=8 .7Hz,1H),6.75(s,1H),6.22(t,J=2.8Hz,1H),6.16(s,1H),3.88(s,3H),3.48(s,3H). 13 C NMR (126MHz, CDCl3): δ160.58,135.71,133.56,128.51,123.97,123.46,118.94,111.26,110.08,107.91,104.10,55.82,34.61.

[0142] Example 16

[0143] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0144]

[0145] 1.0 equivalent of 2-cyanophenyl ether-derived dibenzothiophene sulfonate (0.2mmol, 96.3mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a white solid (36.6mg, 81%) was obtained by rapid column chromatography.

[0146] 1 H NMR (500MHz, CDCl3): δ7.56 (d, J=1.5Hz, 1H), 7.53 (dd, J=8.5, 1.8Hz, 1H), 6.98 (d, J=8.7Hz ,1H),6.71(s,1H),6.18(s,2H),4.19(q,J=7.0Hz,2H),3.62(s,3H),1.51(t,J=7.0Hz,3H). 13 C NMR (126MHz, CDCl3): δ159.43,134.51,133.46,131.99,126.26,123.93,116.38,112.27,108.94,107.93,102.08,64.84,34.91,14.53. HRMS(EI)m / z calcdfor C 14 H 14 N2O[M] + :226.1106,found 226.1096.

[0147] Embodiment 17

[0148] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 2:

[0149]

[0150] 1.0 equivalent of 2-methoxybenzaldehyde-derived 3,7-di-tert-butyldibenzothiophene sulfonate (0.2mmol, 116.3mg), S-rubicene (0.002mmol, 1.8mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a green solid (16.7mg, 39%) was obtained by rapid column chromatography.

[0151] 1 H NMR (500MHz, CD3CN): δ10.44(s,1H),7.74(d,J=2.3Hz,1H),7.66(dd,J=8.7,2.4Hz,1H),7.19(d,J=8.6Hz ,1H),6.73(t,J=2.5Hz,1H),6.15(dd,J=3.4,1.9Hz,1H),6.09(t,J=3.0Hz,1H),3.96(s,3H),3.61(s,3H). 13 C NMR (126MHz, CD3CN): δ190.15,161.75,136.88,133.60,128.25,127.13,125.57,124.90,113.66,109.31,108.48,56.83,35.41. HRMS(EI)m / z calcd for C 13 H 13 NO2[M] + :215.0946,found 215.0937.

[0152] Embodiment 18

[0153] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 3:

[0154]

[0155] 1.0 equivalent of mesitylene-derived dibenzothiophene sulfonate (0.2mmol, 90.8mg), rubicene (0.004mmol, 1.5mg), and biboric acid pinacol ester (1.0mmol, 259.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.8mL) were added. After irradiation with a 40-watt blue light LED (427 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow oily liquid (33.7mg, 69%) was obtained by rapid column chromatography.

[0156] 1 H NMR (500MHz, CDCl3): δ6.77(s,2H),2.37(s,6H),2.24(s,3H),1.37(s,12H). 13 CNMR (126MHz, CDCl3): δ142.08,138.87,127.40,83.40,24.91,22.16,21.20.

[0157] Embodiment 19

[0158] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 3:

[0159]

[0160] 1.0 equivalent of isopropylbenzene-derived dibenzothiophene sulfonate (0.2mmol, 90.9mg), rubicene (0.004mmol, 1.5mg), and biboronic acid pinacol ester (1.0mmol, 259.5mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.8mL) were added. After irradiation with a 40-watt blue LED (427 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow solid (34.5mg, 70%) was obtained by rapid column chromatography.

[0161] 1 H NMR (500MHz, CDCl3): δ7.75 (d, J = 7.7Hz, 2H), 7.24 (d, J = 7.8Hz, 2H), 2.91 (p, J = 6.9Hz, 1H), 1.33 (s, 12H), 1.25 (d, J = 6.9Hz, 6H). 13C NMR (126MHz, CDCl3): δ152.30, 134.91, 125.89, 83.59, 34.33, 24.83, 23.82.

[0162] Embodiment 20

[0163] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 3:

[0164]

[0165] 1.0 equivalent of cyclohexylbenzene-derived dibenzothiophene sulfonate (0.2mmol, 98.7mg), rubicene (0.004mmol, 1.5mg), and biboric acid pinacol ester (1.0mmol, 259.4mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.8mL) were added. After irradiation with a 40-watt blue light LED (427 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and an orange solid (46.9mg, 82%) was obtained by rapid column chromatography.

[0166] 1 H NMR (500MHz, CDCl3): δ7.74(d,J=7.9Hz,2H),7.22(d,J=7.9Hz,2H),2.53-2.48(m ,1H),1.85(t,J=12.9Hz,4H),1.44-1.37(m,4H),1.33(s,12H),1.29-1.24(m,2H). 13 C NMR (126MHz, CDCl3): δ151.47, 134.87, 126.32, 83.57, 44.84, 34.23, 26.84, 26.13, 24.82.

[0167] Embodiment 21

[0168] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 3:

[0169]

[0170] 1.0 equivalent of biphenyl-derived dibenzothiophene sulfonate (0.2mmol, 97.5mg), rubicene (0.004mmol, 1.5mg), and biboric acid pinacol ester (1.0mmol, 259.4mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.8mL) were added. After irradiation with a 40-watt blue LED (427 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a white solid (42.0mg, 75%) was obtained by rapid column chromatography.

[0171] 1 H NMR (500MHz, CDCl3): δ7.89 (d, J = 7.9 Hz, 2H), 7.63 (d, J = 3.6 Hz, 2H), 7.61 (d, J = 4.3 Hz, 2H), 7.45 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.3 Hz, 1H), 1.37 (s, 12H). 13 C NMR (126MHz, CDCl3): δ143.85, 140.97, 135.23, 128.73, 127.52, 127.19, 126.43, 83.79, 24.85.

[0172] Embodiment 22

[0173] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 3:

[0174]

[0175] 1.0 equivalent of iodobenzene-derived dibenzothiophene sulfonate (0.2mmol, 107.5mg), rubicene (0.004mmol, 1.5mg), and biboric acid pinacol ester (1.0mmol, 259.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.8mL) were added. After irradiation with a 40-watt blue LED (427 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and an orange solid (38.3mg, 58%) was obtained by rapid column chromatography.

[0176] 1H NMR (500MHz, CDCl3): δ7.72 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.1 Hz, 2H), 1.33 (s, 12H). 13 C NMR (126MHz, CDCl3): δ136.91, 136.26, 98.81, 84.03, 24.84.

[0177] Embodiment 23

[0178] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 3:

[0179]

[0180] 1.0 equivalent of 1,2-dichlorobenzene-derived dibenzothiophene sulfonate (0.2mmol, 96.3mg), rubicene (0.004mmol, 1.5mg), and biboronic acid pinacol ester (1.0mmol, 259.4mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.8mL) were added. After irradiation with a 40-watt blue LED (427 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and an orange liquid (38.2mg, 70%) was obtained by rapid column chromatography.

[0181] 1 H NMR (500MHz, CDCl3): δ7.86 (s, 1H), 7.59 (d, J = 7.9 Hz, 1H), 7.44 (d, J = 8.2 Hz, 1H), 1.34 (s, 12H). 13 C NMR (126MHz, CDCl3): δ136.55, 135.49, 133.74, 132.25, 130.00, 84.33, 24.83.

[0182] Embodiment 24

[0183] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 3:

[0184]

[0185] 1.0 equivalent of thiophene-derived dibenzothiophene sulfonate (0.2mmol, 83.5mg), rubicene (0.004mmol, 1.5mg), and biboronic acid pinacol ester (1.0mmol, 259.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.8mL) were added. After irradiation with a 40-watt blue light LED (427 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and an orange liquid (17.6mg, 42%) was obtained by rapid column chromatography.

[0186] 1 H NMR (500MHz, CDCl3): δ7.66 (d, J = 2.4 Hz, 1H), 7.64 (d, J = 4.6 Hz, 1H), 7.19 (t, J = 3.6 Hz, 1H), 1.35 (s, 12H). 13 C NMR (126MHz, CDCl3): δ137.14, 132.35, 128.20, 84.07, 24.76.

[0187] Embodiment 25

[0188] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 4:

[0189]

[0190] 1.0 equivalent of 2-methoxybenzoic acid methyl ester-derived dibenzothiophene sulfonate (0.2mmol, 100.1mg), S-rubicene (0.004mmol, 3.4mg), diphenyl disulfide (1.0mmol, 220.6mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow liquid (50.2mg, 92%) was obtained by rapid column chromatography.

[0191] 1H NMR (500MHz, CD3CN): δ7.75 (d, J=2.6Hz, 1H), 7.58 (dd, J=8.7, 2.3Hz, 1H), 7.31- 7.28(m,2H),7.23-7.20(m,3H),7.10(d,J=8.8Hz,1H),3.85(s,3H),3.79(s,3H). 13 CNMR (126MHz, CD3CN): δ166.64,159.73,139.23,138.23,136.69,130.27,129.96,127.58,125.47,122.68,114.68,56.83,52.67.

[0192] Embodiment 26

[0193] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 4:

[0194]

[0195] 1.0 equivalent of 2-cyanophenyl ether-derived dibenzothiophene sulfonate (0.2mmol, 96.3mg), S-rubicene (0.004mmol, 3.4mg), and diphenyl disulfide (1.0mmol, 220.6mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a white solid (41.4mg, 81%) was obtained by rapid column chromatography.

[0196] 1 H NMR (500MHz, CD3CN): δ7.68(s,1H),7.62(d,J=8.9Hz,1H),7.34-7.31(m,2H),7.27( d, J=6.8Hz, 3H), 7.11 (d, J=8.9Hz, 1H), 4.19 (q, J=6.9Hz, 2H), 1.42 (t, J=6.9Hz, 3H). 13 C NMR (126MHz, CDCl3): δ160.18,138.38,137.33,135.87,130.06,129.32,127.13,126.76,115.71,113.04,103.16,65.01,14.45. HRMS(EI)m / zcalcd for C 15H 13 NOS[M] + :255.0718,found 255.0707.

[0197] Embodiment 27

[0198] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 4:

[0199]

[0200] 1.0 equivalent of 2-methoxybenzaldehyde-derived 3,7-di-tert-butyldibenzothiophene sulfonate (0.2mmol, 116.3mg), S-rubicene (0.004mmol, 3.4mg), and diphenyl disulfide (1.0mmol, 220.6mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a brown solid (15.2mg, 31%) was obtained by rapid column chromatography.

[0201] 1 H NMR (500MHz, CD3CN): δ10.36(s,1H),7.73(d,J=2.5Hz,1H),7.66(dd,J=8.8,2.6H z,1H),7.33-7.30(m,2H),7.28-7.25(m,3H),7.17(d,J=8.7Hz,1H),3.94(s,3H). 13 CNMR (126MHz, CD3CN): δ189.56,162.76,141.12,137.61,132.88,130.70,130.37,127.95,127.02,126.49,114.95,57.00. HRMS(EI)m / z calcd for C 14 H 12 O2S[M] + :244.0558,found244.0547.

[0202] Embodiment 28

[0203] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 4:

[0204]

[0205] 1.0 equivalent of 1,2-dimethoxybenzene-derived dibenzothiophene sulfonate (0.2mmol, 94.3mg), S-rubicene (0.004mmol, 3.4mg), and diphenyl disulfide (1.0mmol, 220.6mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and an orange liquid (31.4mg, 64%) was obtained by rapid column chromatography.

[0206] 1 H NMR (500MHz, CD3CN): δ7.28 (t, J = 7.6 Hz, 2H), 7.21-7.17 (m, 3H), 7.05-7.03 (m, 2H), 6.95 (d, J = 8.0 Hz, 1H), 3.81 (s, 3H), 3.76 (s, 3H). 13 C NMR (126MHz, CD3CN): δ150.82,150.75,139.18,130.13,129.26,127.52,127.08,125.10,117.85,113.36,56.49,56.44.

[0207] Embodiment 29

[0208] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 4:

[0209]

[0210] 1.0 equivalent of biphenyl-derived dibenzothiophene sulfide (0.2mmol, 97.5g), S-rubicene (0.004mmol, 3.4mg), diphenyl disulfide (1.0mmol, 220.6mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a white solid (39.9mg, 76%) was obtained by rapid column chromatography.

[0211] 1H NMR (500MHz, CD3CN): δ7.63 (t, J = 8.1 Hz, 4H), 7.46 (t, J = 7.6 Hz, 2H), 7.41-7.32 (m, 8H). 13 C NMR (126MHz, CD3CN): δ140.84,140.81,136.23,135.89,132.23,132.18,130.48,129.95,128.82,128.67,128.52,127.77.

[0212] Embodiment 30

[0213] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 4:

[0214]

[0215] 1.0 equivalent of 2-methoxybenzoic acid methyl ester-derived dibenzothiophene sulfonate (0.2mmol, 99.9mg), S-rubicene (0.004mmol, 3.4mg), and dipyridine disulfide (1.0mmol, 221.4mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a white solid (31.1mg, 57%) was obtained by rapid column chromatography.

[0216] 1 H NMR (500MHz, CDCl3): δ8.40(d,J=4.5Hz,1H),8.04(d,J=2.3Hz,1H),7.71(dd,J=8.6,2.4Hz,1H),7.45(td,J=7.9 ,1.7Hz,1H),7.05(d,J=8.7Hz,1H),6.98(dd,J=7.2,5.0Hz,1H),6.83(d,J=8.0Hz,1H),3.95(s,3H),3.88(s,3H). 13 C NMR (126MHz, CDCl3): δ165.64,161.61,159.99,149.47,140.88,139.00,136.77,121.29,121.13,120.69,119.77,113.24,56.19,52.18.

[0217] Embodiment 31

[0218] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 4:

[0219]

[0220] 1.0 equivalent of 2-methoxybenzoic acid methyl ester-derived dibenzothiophene sulfonate (0.2mmol, 99.9mg), S-rubicene (0.004mmol 3.4mg), dithiophene disulfide (1.0mmol, 237.7mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (17.5mg, 31%) was obtained by rapid column chromatography.

[0221] 1 H NMR (500MHz, CDCl3): δ7.78(d,J=2.5Hz,1H),7.41(d,J=1.5Hz,1H),7.40(dd,J=3.0,1.8Hz, 1H), 7.24 (d, J = 3.1Hz, 1H), 7.02 (dd, J = 5.4, 3.5Hz, 1H), 6.90 (d, J = 8.7Hz, 1H), 3.87 (s, 6H). 13 C NMR (126MHz, CDCl3): δ165.95,158.28,134.61,134.52,133.01,132.68,130.59,128.56,127.77,120.68,112.91,56.19,52.17. HRMS(EI)m / zcalcd for C 13 H 12 O3S2[M] + :280.0228,found 280.0222.

[0222] Embodiment 32

[0223] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 4:

[0224]

[0225] 1.0 equivalent of 2-methoxybenzoic acid methyl ester-derived dibenzothiophene sulfonate (0.2mmol, 99.9mg), S-rubicene (0.004mmol, 3.4mg), dimethyl disulfide (1.0mmol, 96.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) and stirring for 35 hours at room temperature, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (16.6mg, 39%) was obtained by rapid column chromatography.

[0226] 1 H NMR (500MHz, CDCl3): δ7.75 (d, J = 2.4Hz, 1H), 7.42 (dd, J = 8.7, 2.4Hz, 1H), 6.93 (d, J = 8.7Hz, 1H), 3.89 (d, J = 1.7Hz, 6H), 2.46 (s, 3H). 13 C NMR (126MHz, CDCl3): δ166.19, 157.52, 133.68, 131.60, 128.91, 120.64, 112.85, 56.22, 52.15, 17.68.

[0227] Embodiment 33

[0228] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 5:

[0229]

[0230] 5.0 equivalents of diphenyl disulfide (1.0 mmol, 220.6 mg), 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester (0.4 mol, 130.5 mg), and Se-rubicene (0.002 mmol, 2.0 mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.0 equivalents of styrene (0.2 mmol, 21.2 mg) and dry acetonitrile (2.0 mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) at room temperature and stirring for 16 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (37.0 mg, 87%) was obtained by rapid column chromatography.

[0231] 1H NMR (500MHz, CD3CN): δ7.37-7.29(m,6H), 7.25-7.19(m,4H), 3.21(t,J=7.5Hz,2H), 2.91(t,J=8.0Hz,2H). 13 C NMR (126MHz, CD3CN): δ141.41, 137.50, 130.01, 129.59, 129.48, 129.39, 127.33, 126.74, 35.96, 35.13.

[0232] Embodiment 34

[0233] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 5:

[0234]

[0235] 5.0 equivalents of diphenyl disulfide (1.0 mmol, 220.6 mg), 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester (0.4 mol, 130.6 mg), and Se-rubicene (0.002 mmol, 2.0 mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.0 equivalents of 4-fluorostyrene (0.2 mmol, 25.8 mg) and dry acetonitrile (2.0 mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) at room temperature and stirring for 16 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (34.7 mg, 75%) was obtained by rapid column chromatography.

[0236] 1 H NMR (500MHz, CD3CN): δ7.36-7.30(m,4H), 7.25-7.19(m,3H), 7.03(t,J=8.4Hz,2H), 3.18(t,J=7.6Hz,2H), 2.89(t,J=7.6Hz,2H). 13 C NMR (126MHz, CD3CN): δ 163.41, 161.48, 137.38 (d, J = 2.5Hz), 131.33 (d, J = 7.8Hz), 130.02, 129.54, 126.79, 115.90 (d, J = 21.2Hz), 35.17, 35.09. 19 F NMR (471MHz, CD3CN): δ-118.50 (d, J=7.8Hz).

[0237] Embodiment 35

[0238] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 5:

[0239]

[0240] 5.0 equivalents of diphenyl disulfide (1.0 mmol, 220.6 mg), 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester (0.4 mol, 130.6 mg), and Se-rubicene (0.002 mmol, 2.0 mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.0 equivalents of 4-trifluoromethylstyrene (0.2 mmol, 34.9 mg) and dry acetonitrile (2.0 mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) at room temperature and stirring for 16 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (54.8 mg, 97%) was obtained by rapid column chromatography.

[0241] 1 H NMR (500MHz, CD3CN): δ7.61 (d, J = 8.1 Hz, 2H), 7.41 (d, J = 8.0 Hz, 2H), 7.37-7.30 (m, 4H), 7.23-7.19 (m, 1H), 3.24 (t, J = 7.4 Hz, 2H), 2.99 (t, J = 7.5 Hz, 2H). 13 C NMR (126MHz, CD3CN): δ146.05,137.10,130.36,130.05,129.73,129.01,128.75,126.93,126.29-125.94(m),35.67,34.73. 19 F NMR (471MHz, CD3CN): δ-62.75.

[0242] Embodiment 36

[0243] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 5:

[0244]

[0245] 5.0 equivalents of diphenyl disulfide (1.0 mmol, 220.5 mg), 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester (0.4 mol, 130.6 mg), and Se-rubicene (0.002 mmol, 1.9 mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.0 equivalents of 4-methoxystyrene (0.2 mmol, 27.1 mg) and dry acetonitrile (2.0 mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) at room temperature and stirring for 16 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a red liquid (45.9 mg, 94%) was obtained by rapid column chromatography.

[0246] 1 H NMR (500MHz, CD3CN): δ7.36-7.30(m,4H),7.19(t,J=7.2Hz,1H),7.15(d,J=8.6Hz,2 H), 6.85 (d, J = 8.6Hz, 2H), 3.75 (s, 3H), 3.17 (t, J = 7.5Hz, 2H), 2.84 (t, J = 8.0Hz, 2H). 13 C NMR (126MHz, CD3CN): δ159.28,137.61,133.33,130.58,129.99,129.39,126.66,114.71,55.80,35.35,35.08.

[0247] Embodiment 37

[0248] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 5:

[0249]

[0250] 5.0 equivalents of 3,3',5,5'-tetrachlorodiphenyl disulfide (1.0mmol, 359.9mg), 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester (0.4mol, 130.6mg), Se-rubicene (0.002mmol, 1.9mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.0 equivalents of styrene (0.2mmol, 21.2mg) and dry acetonitrile (2.0mL) were added. After irradiation with a 40-watt blue light LED (440 nanometers) at room temperature and stirring for 16 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a colorless liquid (54.4mg, 96%) was obtained by rapid column chromatography.

[0251] 1 H NMR (500MHz, CD3CN): δ7.30 (t, J=7.5Hz, 2H), 7.25-7.21 (m, 6H), 3.26 (t, J=7.5Hz, 2H), 2.93 (t, J=7.5Hz, 2H). 13 C NMR (126MHz, CD3CN): δ142.27, 140.87, 135.89, 129.62, 129.41, 127.47, 126.57, 126.08, 35.47, 34.52. HRMS(EI)m / z calcd for C 14 H 12 Cl2S[M] + :282.0037,found 282.0028.

[0252] Embodiment 38

[0253] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, described in this embodiment is method 5:

[0254]

[0255] 5.0 equivalents of dithiophene disulfide (1.0 mmol, 237.8 mg), di-tert-butyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (0.4 mol, 130.6 mg), and Se-rubicene (0.002 mmol, 1.9 mg) were placed in a reaction bottle. After replacing nitrogen three times, 1.0 equivalents of styrene (0.2 mmol, 21.2 mg) and dry acetonitrile (2.0 mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 16 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow liquid (27.9 mg, 64%) was obtained by rapid column chromatography.

[0256] 1 H NMR (500MHz, CD3CN): δ7.48-7.47(m,1H),7.31-7.28(m,2H),7.23-7.20(m,3H),7.17-7.1 6 (m, 1H), 7.04 (dd, J = 5.4, 3.5Hz, 1H), 3.06 (dd, J = 8.4, 6.8Hz, 2H), 2.88 (t, J = 8.0Hz, 2H). 13C NMR (126MHz, CD3CN): δ141.14, 135.14, 134.57, 130.52, 129.65, 129.40, 128.85, 127.31, 40.65, 36.26.

[0257] Embodiment 39

[0258] A method for synthesizing new CC bonds and CX bonds catalyzed by an organic photoredox catalyst is used in the post-modification of drugs. This embodiment is the post-modification of Fenofibrate:

[0259]

[0260] 1.0 equivalent of fenofibrate-derived dibenzothiophene sulfonate (0.2mmol, 138.9mg), S-rubicene (0.002mmol, 1.9mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction bottle. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 326.1mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow solid (18.9mg, 22%) was obtained by rapid column chromatography.

[0261] 1 H NMR (500MHz, CDCl3): δ7.76(d,J=2.1Hz,1H),7.73(d,J=8.4Hz,3H),7.45(d,J=8.4Hz,2H),6.83(d,J=8.5Hz,1H),6.73( s,1H),6.20-6.19(m,1H),6.13(d,J=2.8Hz,1H),5.08(p,J=6.2Hz,1H),3.58(s,3H),1.55(s,6H),1.21(d,J=6.3Hz,6H). 13 C NMR (126MHz, CDCl3): δ194.15,173.06,157.52,138.41,136.25,134.91,131.12,130.78,130.3 6,130.23,128.56,124.93,122.83,115.52,109.51,107.44,80.02,69.34,34.81,25.18,21.55.

[0262] Embodiment 40

[0263] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst for post-modification of drugs. This embodiment is post-modification of salicin pentaacetate:

[0264]

[0265] 1.0 equivalent of salicin pentaacetate-derived dibenzothiophene sulfonate (0.2mmol, 166.1mg), S-rubicene (0.002mmol, 1.9mg), potassium acetate (1.0mmol, 100.3mg) were placed in a reaction flask. After replacing nitrogen three times, 20.0 equivalents of N-methylpyrrole (4.0mmol, 325.9mg) and dry dimethyl sulfoxide (1.0mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow liquid (105.9mg, 92%) was obtained by rapid column chromatography.

[0266] 1 H NMR (500MHz, CDCl3): δ7.37(s,1H),7.29(d,J=8.4Hz,1H),7.10(d,J=8.3Hz,1H),6.70(s,1H),6.17(s,2H),5.32(d,J=6.3Hz,2H),5.21-5.17(m,2H) ,5.11-5.08(m,2H),4.29(dd,J=11.9,4.8Hz,1H),4.20(d,J=11.5Hz,1H), 3.88(s,1H),3.62(s,3H),2.10(d,J=5.4Hz,6H),2.08(s,3H),2.05(s,6H). 13 C NMR (126MHz, CDCl3): δ170.64,170.50,170.19,169.34,169.26,153.32,133.50,129.72,129.54,128.78,126.12 ,123.55,115.65,108.57,107.73,99.25,72.57,72.01,70.94,68.27,61.86,60.92,34.89,20.92,20.63,20.57.

[0267] Embodiment 41

[0268] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst for post-modification of drugs. This embodiment is post-modification of Clofibrate:

[0269]

[0270] 1.0 equivalent of Clofibrate-derived dibenzothiophene sulfonate (0.2mmol, 115.3mg), S-rubicene (0.004mmol, 3.4mg), and diphenyl disulfide (1.0mmol, 220.6mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow liquid (21.1mg, 30%) was obtained by rapid column chromatography.

[0271] 1 H NMR (500MHz, CDCl3): δ7.44(d,J=7.6Hz,2H),7.39-7.33(m,3H),7.00(d,J=8.9Hz,1H),6.8 5 (s, 1H), 6.69 (d, J = 8.4Hz, 1H), 4.25 (q, J = 7.2Hz, 2H), 1.57 (s, 6H), 1.27 (t, J = 7.1Hz, 3H). 13 C NMR (126MHz, CDCl3): δ173.96,151.13,133.39,132.58,131.81,129.46,128.89,128.24,127.56,126.33,118.28,80.50,61.56,24.93,14.09. HRMS(EI)m / zcalcd for C 18 H 19 ClO3S[M] + :350.0743, found 350.0735.

[0272] Embodiment 42

[0273] A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst is used in the post-modification of drugs. This embodiment is the post-modification of Gemfibrozil methyl ester:

[0274]

[0275] 1.0 equivalent of Gemfibrozil methyl ester-derived dibenzothiophene sulfonate (0.2mmol, 119.5mg), S-rubicene (0.004mmol, 3.4mg), and diphenyl disulfide (1.0mmol, 220.6mg) were placed in a reaction bottle. After replacing nitrogen three times, 5.0 equivalents of pyridine (1.0mmol, 80.0mg) and dry acetone (0.4mL) were added. After irradiation with a 40-watt blue LED (440 nanometers) at room temperature and stirring for 35 hours, dichloromethane and silica gel powder were added to the reaction system, and then the organic solvent was removed under reduced pressure, and a yellow liquid (55.0mg, 74%) was obtained by rapid column chromatography.

[0276] 1 H NMR (500MHz, CDCl3): δ7.29(s,1H),7.19(t,J=7.7Hz,2H),7.08(t,J=7.4Hz,1H),7.01(d,J=7.7Hz,2H),6 .72(s,1H),3.95(t,J=5.5Hz,2H),3.67(s,3H),2.33(s,3H),2.17(s,3H),1.79-1.71(m,4H),1.23(s,6H). 13 C NMR (126MHz, CDCl3): δ178.17,157.87,141.09,138.91,138.20,128.75,126.46,125. 34,124.81,121.17,113.10,67.97,51.69,42.04,37.01,25.15,25.07,20.84,15.49. HRMS(EI)m / z calcd for C 22 H 28 O3S[M] + :372.1759, found 372.1747.

[0277] Although the embodiments of the present invention are disclosed for illustrative purposes, those skilled in the art will appreciate that various substitutions, changes and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. Therefore, the scope of the present invention is not limited to the contents disclosed in the embodiments.

Claims

1. A method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst, characterized in that: This includes any of the following methods: Method 1: Using aryl sulfide and [CuCF3] as reaction materials, trifluoromethylation of aryl sulfide is achieved under catalyst, solvent and light conditions; wherein the catalyst is S-rubicene, acetone is used as solvent, and 40 watt blue light LED is used to irradiate the aryl sulfide at room temperature to achieve trifluoromethylation; Or method 2: using an aryl sulfide salt and a heteroaromatic ring compound as reaction raw materials, achieving heteroarylation of the aryl sulfide salt under the conditions of a catalyst, a base, a solvent, and light; wherein the catalyst is S-rubicene, the base is potassium acetate, dimethyl sulfoxide is used as the solvent, and the aryl sulfide salt is irradiated with a 40-watt blue light LED at room temperature to achieve heteroarylation; Or method 3: using aryl sulfide and biboric acid pinacol ester as reaction raw materials, borate esterification of aryl sulfide is achieved under the conditions of catalyst, organic base, solvent and light; wherein the catalyst is rubicene, the organic base is pyridine, acetone is used as solvent, and 40 watt blue light LED is used to irradiate the aryl sulfide at room temperature; Or method 4: using an aryl sulfide and a disulfide as the reaction raw materials, and realizing the thioetherification of the aryl sulfide under the conditions of a catalyst / organic base, a solvent, and light; wherein the catalyst is S-rubicene, the organic base is pyridine, acetone is used as the solvent, and the thioetherification of the aryl sulfide is realized under room temperature conditions by irradiation with a 40-watt blue light LED; Or method 5: using aromatic vinyl and disulfide as reaction raw materials, realizing the thioetherification of aromatic vinyl under the conditions of catalyst, organic base, solvent and light; wherein the catalyst is Se-rubicene, the organic base is 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester, using acetonitrile as solvent, realizing the thioetherification of aromatic vinyl under room temperature conditions by irradiation with a 40-watt blue light LED.

2. The method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst according to claim 1, characterized in that: The general reaction formulas of method 1, method 2, method 3, method 4 and method 5 are as follows: Method 1: Method 2: Wherein, X is a heteroatom, including but not limited to O, S, Se, and N; Method 3: Method 4: Method 5: Wherein, Ar1 represents different aromatic systems; X represents a heteroatom, including but not limited to O, S, Se, Te, and N; and R represents different aromatic, heteroaromatic or alkyl systems.

3. The method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst according to claim 2, characterized in that: The structural formula of hong is shown below:

4. The method for synthesizing new CC bonds and CX bonds catalyzed by an organic photoredox catalyst according to claim 3, characterized in that: The aryl sulfide salt is any one of the following compounds: The aromatic vinyl is any one of the following compounds: Wherein, R, R1, and R2 are independent C1-C15 alkyl chains, and the C1-C15 alkyl chains include straight-chain alkyl groups with a total number of carbon atoms of 1 to 15, branched-chain alkyl groups with a total number of carbon atoms of 3 to 15, or cycloalkyl groups with a total number of carbon atoms of 3 to 8.

5. The method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst according to claim 4, characterized in that: The straight-chain alkyl group having a total carbon atom count of 1 to 15 includes: n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n-pentadecyl; The branched alkyl group having a total of 3 to 15 carbon atoms includes isopropyl, tert-butyl, 2-methylpropyl, 2-methylbutyl, 3-ethylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2-methylundecyl, 2-methyldodecyl, 2-methyltridecyl, 2-methyltetradecyl, 3-ethylpentyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, 3-ethylundecyl, 3-ethyldodecyl and 3-ethyltridecyl; The cycloalkyl group having 3 to 8 carbon atoms includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

6. The method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst according to claim 5, characterized in that: The heteroaromatic compound is any one of the following compounds:

7. The method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst according to claim 6, characterized in that: The disulfide is any one of the following compounds: Wherein, R is an independent C1-C15 alkyl chain, and the C1-C15 alkyl chain includes a straight chain alkyl group with a total carbon atom number of 1-15, a branched chain alkyl group with a total carbon atom number of 3-15, or a cycloalkyl group with a total carbon atom number of 3-8.

8. The method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst according to claim 7, characterized in that: The method 1, method 2, method 3, method 4 and method 5 comprise the following steps: Method 1: (1) Using inert gas protection, under the catalytic action of S-rubicene, aryl sulfide salt and [CuCF3] are placed in acetone, and reacted at room temperature under the irradiation of blue light LED to obtain a mixture; (2) adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter; Method 2: (1) using inert gas protection, under the catalytic action of S-rubicene, adding potassium acetate as an additive, placing an aryl sulfide salt and a heteroaromatic ring compound in dimethyl sulfoxide, reacting at room temperature under the irradiation of a blue light LED to obtain a mixture; (2) adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter; Method 3: (1) using inert gas protection, under the catalytic action of rubicene, adding pyridine as an additive, placing aryl sulfide salt and biboric acid pinacol ester in acetone, reacting at room temperature under the irradiation of blue light LED to obtain a mixture; (2) adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter; Method 4: (1) Using inert gas protection, under the catalytic action of S-rubicene, adding pyridine as an additive, placing the aryl sulfide and the disulfide in acetone, reacting at room temperature under the irradiation of a blue LED to obtain a mixture; (2) adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter; Method 5: (1) Under inert gas protection, under the catalytic action of Se-rubicene, 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid di-tert-butyl ester is added as an additive, aromatic vinyl and disulfide are placed in acetonitrile, and reacted at room temperature under the irradiation of blue LED to obtain a mixture; (2) Adding dichloromethane and silica gel powder to the reaction system, then removing the organic solvent under reduced pressure, and finally obtaining a pure product through a rapid column filter.

9. The method for synthesizing new CC bonds and CX bonds using an organic photoredox catalyst according to claim 8, characterized in that: The method 1, method 2, method 3, method 4 and method 5 specifically include the following steps: Method 1: 1.0 equivalent of aryl sulfide salt, 1.5 equivalent of [CuCF3], and S-rubicene are placed in a reaction bottle, and the amount of S-rubicene added is 1.0 mol% of the total molar amount of aryl sulfide salt; after replacing nitrogen three times, dry acetone is added to keep the concentration of the solution at 0.025 M; after stirring for 12 hours at room temperature under 40-watt blue light LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained by rapid column chromatography; Method 2: 1.0 equivalent of aryl sulfide, 5.0 equivalent of potassium acetate and S-rubicene are placed in a reaction bottle, and the amount of S-rubicene added is 1.0 mol% of the total molar amount of aryl sulfide; after replacing nitrogen three times, 20.0 equivalents of heteroaromatic hydrocarbons are added; dry dimethyl sulfoxide is added to keep the concentration of the solution at 0.2 M; after stirring for 35 hours at room temperature under 40-watt blue LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained by rapid column chromatography; Method 3: 1.0 equivalent of aryl sulfide salt, 5.0 equivalent of biboric acid pinacol ester and rubicene are placed in a reaction bottle, and the amount of rubicene added is 2.0 mol% of the total molar amount of aryl sulfide salt; after replacing nitrogen three times, 5.0 equivalent of pyridine is added; dry acetone is added to keep the concentration of the solution at 0.25M; after stirring for 35 hours at room temperature under 40-watt blue light LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained by rapid column chromatography; Method 4: 1.0 equivalent of aryl sulfide, 5.0 equivalent of disulfide and S-rubicene are placed in a reaction bottle, and the amount of S-rubicene added is 2.0 mol% of the total molar amount of aryl sulfide; after replacing nitrogen three times, 5.0 equivalent of pyridine is added; dry acetone is added to keep the concentration of the solution at 0.5 M; after stirring for 35 hours at room temperature under 40-watt blue LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained by rapid column chromatography; Method 5: 5.0 equivalents of disulfide, 2.0 equivalents of di-tert-butyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate and Se-rubicene are placed in a reaction bottle, and the amount of Se-rubicene added is 1.0 mol% of the total molar amount of aromatic vinyl; after replacing nitrogen three times, 1.0 equivalent of aromatic vinyl is added; dry acetonitrile is added to keep the concentration of the solution at 0.1 M; after stirring for 28 hours at room temperature under 40-watt blue light LED irradiation, dichloromethane and silica gel powder are added to the reaction system, and then the organic solvent is removed under reduced pressure, and finally the pure product is obtained through a rapid column machine.

10. Use of the synthetic method for constructing new CC bonds and CX bonds catalyzed by an organic photoredox catalyst as claimed in any one of claims 1 to 9 in the post-modification of drugs.

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