A method for preparing a carborane thioether compound by a carborane hydrosulfurization reaction of an olefin

Abstract

The application discloses a method for preparing a carborane sulfide compound through a carbon borane sulfhydryl reaction of an olefin, and the method uses a carborane thiol and a non-activated olefin as raw materials, and generates the carborane sulfide through a free radical addition reaction of the carborane thiol and the olefin under the catalysis of a photosensitizer and through light irradiation. The carborane sulfide is prepared through a photo reaction, raw materials are cheap and easy to obtain, operation is simple, the reaction is mild, conditions are safe, the synthesis yield is high, and side reactions are few, so that the method is an economic and environment-friendly synthesis route, provides a new path for synthesizing the carborane sulfide, and can be suitable for industrialized production.

Description

Technical Field

[0001] This invention relates to the fields of organic chemical synthesis and pharmaceuticals, and particularly to a carborane sulfide compound and its preparation method. Background Technology

[0002] Malignant tumors seriously endanger human life, and conventional radiation oncology treatments, while effective in treating tumors, also cause some damage to normal cells. In 1936, Gordon Locher first proposed boron neutron capture therapy (BNCT) for cancer treatment. The principle of boron neutron capture therapy is based on the use of non-radioactive elements... 10 After B captures a thermal neutron, it undergoes nuclear fission to produce alpha particles and... 7 Both lithium atoms and other radioactive materials are high-energy-density rays with penetrating power, but their penetration is limited to the diameter of a single cell. This means they kill only tumor cells without affecting normal tissues. Boron-neutron capture therapy (BNCT) is a dual-mode, cell-level, highly targeted, and precise radiotherapy. It consists of two processes: boron drug delivery and neutron irradiation. Currently, the development of linear accelerator neutron sources has effectively solved the neutron irradiation technology problem, so the current limitation on the development of boron neutron capture therapy mainly focuses on the boron drug delivery process.

[0003] Currently, BNCT (Boron-Neurotransferase) is not widely used in tumor treatment, mainly due to the limited number of boron carriers available for clinical trials. Ultimately, this stems from the underdeveloped nature of carborane functionalization methods, making it difficult to effectively introduce carboranes into biomolecules. Current methods for constructing carborane functionalization primarily include: directly activating the BH bond of carborane, but this method struggles to control the reaction site, and selective control remains a significant challenge. Another approach is to pre-activate the BH bond of carborane before functionalization, which allows for effective control of the reaction site. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing carborane sulfide compounds to solve the problems of carborane functionalization at present.

[0005] In a first aspect, the present invention provides a method for preparing a carborane sulfide compound, comprising:

[0006] The step involves preparing carborane sulfide compounds by reacting unactivated olefins with carborane thiols (R4-SH) via visible-light photocatalytic radical addition reaction in the presence of a photosensitizer.

[0007]

[0008] Where R1 is H, R3 is H, and R2 is C1-C 10The alkyl group, halogen-substituted alkyl group, functionalized alkyl group, or functionalized aryl group, wherein the functionalized alkyl group or functionalized aryl group is selected from any of the following groups:

[0009]

[0010] R1 is CH3, R3 is hydrogen, and R2 is a C5 straight-chain alkane;

[0011] R1 is H, R3 is methyl, and R2 is OAc or CH2OH;

[0012] The carborane thiol compound R4-SH can be selected from any of the following:

[0013]

[0014] Preferably, the reaction is carried out in an organic solvent system, which can be any one of acetonitrile, trifluorotoluene, ethyl acetate, ethanol, dichloromethane, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, hexafluoroisopropanol, tetrahydrofuran, methanol, and dichloroethane. Trifluorotoluene is preferred.

[0015] Preferably, the photosensitizer is an iridium photosensitizer, which can be selected from any one of (Ir[dF(CF3)ppy]2(dtbpy))PF6, [Ir{dFCF3ppy}2(bpy)]PF6, and Ir(ppy)3, with (Ir[dF(CF3)ppy]2(dtbpy))PF6 being the most preferred.

[0016] Preferably, the molar ratio of carborane thiol compound R4-SH, non-activated olefin, and photosensitizer is 1 to 2:1:0.01, more preferably 1.8:1:0.01.

[0017] Preferably, the visible light catalytic radical addition reaction refers to the reaction under visible light irradiation for a reaction time of more than 1 hour, preferably 12 hours.

[0018] Compared with the prior art, the technical advantages of the present invention are as follows:

[0019] (1) This invention uses readily available carborane thiols and non-activated olefins as starting materials. Under the action of iridium photosensitizer, carborane thioether compounds are synthesized by direct free radical addition reaction catalyzed by visible light. Among them, the non-activated olefins with different functional groups add to various carborane thiols, with the yield reaching more than 93%. Moreover, the reaction conditions are simple and mild, the starting materials are readily available, the reaction is highly efficient, and the production cost is low, making it suitable for industrial production. Attached Figure Description

[0020] The technical solution and other beneficial effects of this application will become apparent from the following detailed description of specific embodiments in conjunction with the accompanying drawings.

[0021] Figure 1 This is the NMR spectrum of the carborane sulfide 1a described in Example 1 of this application.

[0022] Figure 2 This is the NMR spectrum of the carborane sulfide 2a described in Example 2 of this application.

[0023] Figure 3 This is the NMR spectrum of the carborane sulfide 3a described in Example 3 of this application.

[0024] Figure 4 This is the NMR spectrum of the carborane sulfide 4a described in Example 4 of this application.

[0025] Figure 5 This is the NMR spectrum of the carborane sulfide 5a described in Example 5 of this application.

[0026] Figure 6 This is the NMR spectrum of the carborane sulfide 6a described in Example 6 of this application.

[0027] Figure 7 This is the NMR spectrum of the carborane sulfide 7a described in Example 7 of this application.

[0028] Figure 8 This is the NMR spectrum of the carborane sulfide 8a described in Example 8 of this application.

[0029] Figure 9 This is the NMR spectrum of the carborane sulfide 9a described in Example 9 of this application.

[0030] Figure 10 This is the NMR spectrum of the carborane sulfide 10a described in Example 10 of this application.

[0031] Figure 11 This is the NMR spectrum of the carborane sulfide 11a described in Example 11 of this application.

[0032] Figure 12 This is the NMR spectrum of the carborane sulfide 12a described in Example 12 of this application.

[0033] Figure 13 This is the NMR spectrum of the carborane sulfide 13a described in Example 13 of this application.

[0034] Figure 14 This is the NMR spectrum of the carborane sulfide 14a described in Example 14 of this application.

[0035] Figure 15 This is the NMR spectrum of the carborane sulfide 15a described in Example 15 of this application.

[0036] Figure 16 This is the NMR spectrum of carborane sulfide 16a described in Example 16 of this application.

[0037] Figure 17 This is the NMR spectrum of the carborane sulfide 17a described in Example 17 of this application.

[0038] Figure 18 This is the NMR spectrum of the carborane sulfide 18a described in Example 18 of this application.

[0039] Figure 19 This is the NMR spectrum of the carborane sulfide 19a described in Example 19 of this application.

[0040] Figure 20 This is the NMR spectrum of the carborane sulfide 20a described in Example 20 of this application.

[0041] Figure 21 This is the NMR spectrum of the carborane sulfide 21a described in Example 21 of this application.

[0042] Figure 22 This is the NMR spectrum of the carborane sulfide 22a described in Example 22 of this application.

[0043] Figure 23 This is the NMR spectrum of the carborane sulfide 23a described in Example 23 of this application. Detailed Implementation

[0044] The present invention will be further described in detail below through specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any way. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are still within the scope of protection of the present invention.

[0045] It should be noted that terms such as "upper", "lower", "left", "right", and "middle" used in this specification are only for clarity of description and are not intended to limit the scope of implementation. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered as within the scope of this application.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the term “and / or” as used herein includes any and all combinations of one or more of the associated listed items.

[0047] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0048] As used herein, the term “about” is used to provide for the flexibility and imprecision associated with a given term, measure, or value. Those skilled in the art can readily determine the degree of flexibility for a particular variable.

[0049] As used herein, the term “at least one of…” is intended to be synonymous with “one or more of…”. For example, “at least one of A, B, and C” explicitly includes only A, only B, only C, and combinations thereof.

[0050] This application provides a carborane sulfide compound and its preparation method. Detailed descriptions follow. It should be noted that the order of description in the following embodiments is not intended to limit the preferred order of embodiments. Furthermore, in the description of this application, various embodiments of the invention may be presented in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 5, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0051] The photosensitizers (Ir[dF(CF3)ppy]2(dtbpy)) PF6 mentioned in the following examples are named [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridineN1,N1']bis[3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridylN]phenyl-C]iridium hexafluorophosphate(III), [Ir{dFCF3ppy}2(bpy)]PF6 is named di[2-(2,4-difluorophenyl)-5-trifluoromethylpyridine][2-2'-bipyridine]iridium di(hexafluorophosphate), Ir(ppy)3 is named tris(2-phenylpyridine)iridium, and 4CzIPN is named 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile, all of which are commercially available products. The carborane thiol compound R4-SH is obtained through carborane (C2B 10 H 12 The reaction of disulfide with disulfide yields disulfide dicarbonborane (C4B) 20 H 22S2) is prepared by reduction with sodium borohydride, wherein the carborane can be any one of ortho-carborane, meta-carborane, or para-carborane, and is a commercially available product.

[0052] Example 1

[0053]

[0054] To a 10 mL Shrek tube, add 22.8 mg (0.2 mmol) of ethyl 3-butenoate, 63.5 mg (0.36 mmol) of o-carborane thiol, 0.01 mmol of Ir[dF(CF3)ppy]2(dtbpy))PF6, and 2 mL of trifluorotoluene solvent. Irradiate the mixture at room temperature for 12 hours to allow for complete reaction. After the reaction, add 100 mg of 200-300 mesh silica gel, stir until homogeneous, and separate by column chromatography with a petroleum ether:ethyl acetate ratio of 10:1 to obtain the corresponding carborane thioether compound 1a (54.1 mg, yield 93%).

[0055] Its NMR spectrum is as follows Figure 1 As shown, the NMR spectrum of product 1a reflects its extremely high purity in terms of shape, signal, and noise, and no other organic impurities were generated during the preparation process.

[0056] Example 2

[0057]

[0058] The rest is the same as in Example 1, except that the unactivated olefin compound is 4-penten-1-ol, yielding 2a (44.9 mg, yield 86%), whose NMR spectrum is shown below. Figure 2 As shown in the figure. The NMR spectrum of 2a, including its shape, signal, and noise, also reflects that the purity of 2a is extremely high, and no other organic impurities were generated during the preparation process.

[0059] Example 3

[0060]

[0061] The rest is the same as in Example 1, except that the non-activated olefin compound is N-allylcarbamate tert-butyl ester, yielding 3a (54.3 mg, yield 81%), whose NMR spectrum is shown below. Figure 3 As shown. The NMR spectrum of 3a, including its shape, signal, and noise, also reflects that the purity of 3a is extremely high, and no other organic impurities were generated during the preparation process.

[0062] Example 4

[0063]

[0064] The rest is the same as in Example 1, except that the unactivated olefin compound is (3-buten-1-ylsulfonyl)benzene, yielding 4a (62.0 mg, yield 83%), whose NMR spectrum is shown below. Figure 4 As shown. The NMR spectrum of 4a, including its shape, signal, and noise, also reflects that the purity of 4a is extremely high, and no other organic impurities were generated during the preparation process.

[0065] Example 5

[0066]

[0067] The rest is the same as in Example 1, except that the unactivated olefin compound is 4-vinylpyridine, yielding 5a (35.9 mg, yield 64%), whose NMR spectrum is shown below. Figure 5 As shown in the figure. The NMR spectrum of 5a, including its shape, signal, and noise, also reflects that the purity of 5a is extremely high, and no other organic impurities were generated during the preparation process.

[0068] Example 6

[0069]

[0070] The rest is the same as in Example 1, except that the non-activated olefin compound is allyltrimethylsilane, yielding 6a (44.2 mg, yield 76%), whose NMR spectrum is shown below. Figure 6 As shown in the figure. The NMR spectrum of 6a, including its shape, signal, and noise, also reflects that the purity of 6a is extremely high, and no other organic impurities were generated during the preparation process.

[0071] Example 7

[0072]

[0073] The rest is the same as in Example 1, except that the unactivated olefin compound is 1-decene, yielding 7a (60.3 mg, 95% yield), whose NMR spectrum is shown below. Figure 7 As shown in the figure. The NMR spectrum of 7a, including its shape, signal, and noise, also reflects that the purity of 7a is extremely high, and no other organic impurities were generated during the preparation process.

[0074] Example 8

[0075]

[0076] The rest is the same as in Example 1, except that the carboranethiol compound is a m-carboranethiol, yielding 8a (44.3 mg, yield 76%), whose NMR spectrum is shown below. Figure 8As shown in the figure. The NMR spectrum of 8a, including its shape, signal, and noise, also reflects that the purity of 8a is extremely high, and no other organic impurities were generated during the preparation process.

[0077] Example 9

[0078]

[0079] The rest is the same as in Example 2, except that the carboranethiol compound is a m-carboranethiol, yielding 9a (42.4 mg, yield 81%), whose NMR spectrum is shown below. Figure 9 As shown in the figure. The NMR spectrum of 9a, including its shape, signal, and noise, also reflects that the purity of 9a is extremely high, and no other organic impurities were generated during the preparation process.

[0080] Example 10

[0081]

[0082] The rest is the same as in Example 1, except that the unactivated olefin compound is 2-(3-cyano-4-isobutoxyphenyl)-4-methylthiazolyl-5-carboxylic acid hept-6-en-1-yl ester, yielding 10a (96.5 mg, yield 84%), whose NMR spectrum is shown below. Figure 10 As shown in the figure. The morphology, signal, and noise of the NMR spectrum of 10a also reflect that the purity of 10a is extremely high, and no other organic impurities are generated during the preparation process.

[0083] Example 11

[0084]

[0085] The rest is the same as in Example 1, except that the unactivated olefin compound is (2-cyclopropyl-4-(4-fluorophenyl)quinoline-3-yl)methylhexyl-5-enoate, yielding 11a (87.0 mg, yield 79%), whose NMR spectrum is shown below. Figure 11 As shown in the figure. The morphology, signal, and noise of the NMR spectrum of 11a also reflect that the purity of 11a is extremely high, and no other organic impurities are generated during the preparation process.

[0086] Example 12

[0087]

[0088] The rest is the same as in Example 1, except that the unactivated olefin compound is N-(pent-4-en-1-yl)-4-(5-(p-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamide, yielding 12a (124.8 mg, 99% yield), whose NMR spectrum is shown below. Figure 12As shown in the figure. The morphology, signal, and noise of the NMR spectrum of 12a also reflect that the purity of 12a is extremely high, and no other organic impurities were generated during the preparation process.

[0089] Example 13

[0090]

[0091] The rest is the same as in Example 1, except that the non-activated olefin compound is 3-(4,5-diphenyloxazol-2-yl)propionate but-3-en-1-yl ester, yielding 13a (79.1 mg, yield 76%), whose NMR spectrum is shown below. Figure 13 As shown in the figure. The morphology, signal, and noise of the NMR spectrum of 13a also reflect that the purity of 13a is extremely high, and no other organic impurities were generated during the preparation process.

[0092] Example 14

[0093]

[0094] The rest is the same as in Example 1, except that the unactivated olefin compound is ((3aS,5aR,8aR,8bS)-2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxonol)[4,5-b:4',5'-d]pyran-3a-yl)methylbut-3-enoate, yielding 14a (72.5 mg, 72% yield), whose NMR spectrum is shown below. Figure 14 As shown, the extremely high purity of 14a can also be seen from the NMR spectrum shape, signal, and noise, and no other organic impurities were generated during the preparation process.

[0095] Example 15

[0096]

[0097] The rest is the same as in Example 1, except that the unactivated olefin compound is (3aR,5R,6S,6aR)-6-(allyloxy)-5-(2,2-dimethyl-1,3-dioxolane-4-yl)-2,2-dimethyltetrahydrofurano[2,3-d][1,3]dioxane, yielding 15a (56.5 mg, 85% yield), 7.24 (1B), -2.45 (1B), and its NMR spectrum is shown below. Figure 15 As shown, the extremely high purity of 15a can also be seen from the NMR spectrum shape, signal, and noise of the 15a, and no other organic impurities were generated during the preparation process.

[0098] Example 16

[0099]

[0100] The rest is the same as in Example 5, except that the carboranethiol compound is a m-carboranethiol, yielding 16a (30.8 mg, yield 54%), whose NMR spectrum is shown below. Figure 16 As shown, the extremely high purity of 16a can also be seen from the NMR spectrum shape, signal, and noise, and no other organic impurities were generated during the preparation process.

[0101] Example 17

[0102]

[0103] The rest is the same as in Example 1, except that the unactivated olefin compound is 1-dodecene, yielding 17a (60.6 mg, 88% yield), whose NMR spectrum is shown below. Figure 17 As shown in the figure. The morphology, signal, and noise of the NMR spectrum of 17a also reflect that the purity of 17a is extremely high, and no other organic impurities were generated during the preparation process.

[0104] Example 18

[0105]

[0106] The rest is the same as in Example 1, except that the unactivated olefin compound is 3-butenonitrile, yielding 18a (41.2 mg, yield 85%), whose NMR spectrum is shown below. Figure 17 As shown. The morphology, signal, and noise of the NMR spectrum of 18a also reflect that the purity of 18a is extremely high, and no other organic impurities were generated during the preparation process.

[0107] Example 19

[0108]

[0109] The rest is the same as in Example 1, except that the unactivated olefin compound is 1-decene, yielding 19a (64.7 mg, 79% yield), whose NMR spectrum is shown below. Figure 19 As shown, the extremely high purity of 19a can also be seen from the NMR spectrum shape, signal, and noise of the 19a, and no other organic impurities were generated during the preparation process.

[0110] Example 20

[0111]

[0112] The rest is the same as in Example 1, except that the unactivated olefin compound is 4-phenyl-1-buten-4-ol, yielding 20a (48.0 mg, yield 74%), whose NMR spectrum is shown below. Figure 20As shown in the figure. The NMR spectrum of 20a, including its shape, signal, and noise, also reflects that the purity of 20a is extremely high, and no other organic impurities were generated during the preparation process.

[0113] Example 21

[0114]

[0115] The rest is the same as in Example 1, except that the unactivated olefin compound is 10-undecenal, yielding 21a (33.7 mg, yield 49%), whose NMR spectrum is shown below. Figure 21 As shown in the figure. The NMR spectrum of 21a, including its shape, signal, and noise, also reflects that the purity of 21a is extremely high, and no other organic impurities were generated during the preparation process.

[0116] Example 22

[0117]

[0118] The rest is the same as in Example 1, except that the non-activated olefin compound is diethyl allyl malonate, yielding 22a (68.0 mg, 90% yield), and its NMR spectrum is shown below. Figure 22 As shown in the figure. The NMR spectrum of 22a, including its shape, signal, and noise, also reflects that the purity of 22a is extremely high, and no other organic impurities were generated during the preparation process.

[0119] Example 23

[0120]

[0121] The rest is the same as in Example 1, except that the non-activated olefin compound is pinacol vinylborate, yielding 23a (30.4 mg, yield 46%), whose NMR spectrum is shown below. Figure 23 As shown in the figure. The NMR spectrum of 23a, including its shape, signal, and noise, also reflects that the purity of 23a is extremely high, and no other organic impurities were generated during the preparation process.

[0122] The yields of the target products prepared in the above embodiments are listed in Table 1.

[0123] Table 1

[0124]

[0125]

[0126] The yields of different molar ratios of carborane thiols R4-SH, non-activated olefins, and photosensitizers in Example 17 are listed in Table 2.

[0127] Table 2

[0128] serial number molar ratio of ortho-boranethiol compounds, non-activated olefins, and photosensitizers 17a yield 1 1.2：1：0.01 78％ 2 1.8：1：0.01 88％ 3 2.0：1：0.01 88％

[0129] The above embodiments provide a method for preparing carborane sulfide compounds. Using inexpensive olefins and carborane thiols as starting materials, trifluorotoluene as a solvent, and (Ir[dF(CF3)ppy]2(dtbpy))PF6) as a photosensitizer, carborane thiols undergo a free radical addition reaction with olefins under visible light catalysis to synthesize carborane sulfide compounds. This method is compatible with most functional groups and shows good compatibility with complex drug molecules with valuable structures, such as carbohydrates, lipids, quinolines, pyrimidines, pyrazoles, oxazoles, and thiazoles. This reaction can introduce carborane into the molecule simply, efficiently, and singly. It provides a new method for the synthesis of carborane drug molecules and boron neutron capture therapy (BNCT) candidate drugs. As shown in Table (1), the carborane substrate of the carborane sulfide compound can be an ortho-carborane thiol or a meta-carborane thiol, and the non-activated olefin substrate of the carborane sulfide compound can be any of the non-activated olefins substituted with different groups.

[0130] This application provides a method for preparing carborane sulfide compounds. Using carborane thiols and unactivated olefins as starting materials, anhydrous trifluorotoluene as solvent, and an iridium catalyst as photosensitizer, the carborane sulfide compounds are synthesized by direct free radical addition reaction under visible light catalysis. The yields can reach 60%-99% or more. Moreover, the reaction conditions are simple and mild, the starting materials are readily available, the reaction is highly efficient, and the production cost is low, making it suitable for industrial production.

[0131] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions of other embodiments.

[0132] The preparation method of a carborane sulfide compound provided in the embodiments of this application has been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the technical solutions and core ideas of this application. Those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A method for preparing a carborane sulfide compound, characterized in that, include: The step of preparing carborane sulfide compounds by reacting unactivated olefins with carborane thiols (R4-SH) via visible-light photocatalytic radical addition reaction under the action of a photosensitizer. wherein R1is H, R3is H, R2is C1-C 10 alkyl, halo-substituted alkyl, functionalized alkyl, or functionalized aryl, the functionalized alkyl or functionalized aryl being selected from any one of the following: R1 is CH3, R3 is hydrogen, and R2 is a C5 straight-chain alkane; R1 is H, R3 is methyl, and R2 is OAc or CH2OH; The carborane thiol compound R4-SH is selected from any one of the following:

2. The method as described in claim 1, characterized in that, The reaction is carried out in an organic solvent system selected from any one of acetonitrile, trifluorotoluene, ethyl acetate, ethanol, dichloromethane, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, hexafluoroisopropanol, tetrahydrofuran, methanol, and dichloroethane, with trifluorotoluene being preferred.

3. The method as described in claim 1, characterized in that, The photosensitizer is an iridium photosensitizer, selected from any one of (Ir[dF(CF3)ppy]2(dtbpy))PF6, [Ir{dFCF3ppy}2(bpy)]PF6, and Ir(ppy)3, with (Ir[dF(CF3)ppy]2(dtbpy))PF6 being preferred.

4. The method as described in claim 1, characterized in that, The molar ratio of carborane thiol compound R4-SH, non-activated olefin, and photosensitizer is 1 to 2:1:0.01, preferably 1.8:1:0.

01.

5. The method as described in claim 1, characterized in that, Visible light catalytic radical addition reaction refers to a reaction under visible light irradiation for a reaction time of more than 1 hour, preferably 12 hours.

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