Tandem cyclization reaction of photocatalytic diallyl compounds

Abstract

The invention relates to a tandem cyclization reaction of photocatalytic diallyl compounds. The invention relates to a photocatalytic cascade cyclization reaction of diallyl compounds, which comprises the following steps: mixing a diallyl compound and a thiosulfonate compound in a solvent, and stirring to react under the conditions of visible light irradiation and room temperature to obtain a bifunctional cyclization product; the diallyl compound is diallyl diethyl malonate or diallyl diphenyl silane, and the diallyl compound is diallyl diethyl malonate or diallyl diphenyl silane. According to the series cyclization reaction of the photocatalytic diallyl compound, the cyclization reaction without participation of a photocatalyst and an additive is completed through visible light induction on the basis of the diallyl compound, and a novel efficient, simple, convenient and environment-friendly bifunctional cyclization strategy is established; regioselective functionalization reaction is completed through different diallyl compounds, generation of by-products is greatly reduced, the yield of target products is improved, and expansibility is improved through wide thiosulfonate substrates.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a photocatalytic tandem cyclization reaction of diallyl compounds. Background Technology

[0002] Heteroatom-containing cyclic compounds are widely found in various compounds, including pharmaceuticals, agrochemicals, and metal catalytic ligands. Therefore, it is essential to develop an efficient, green, and mild photochemical method to synthesize heteroatom-containing cyclic compounds.

[0003] In past research, some teams have used metal-catalyzed pathways for cyclization via variable-valence metals or expensive photocatalysts. However, these methods typically require costly metal catalysts and corresponding ligands, or additional additives. Therefore, radical tandem cyclization processes under visible light conditions have gradually developed, due to the avoidance of expensive metal catalysts and the mild, green catalytic conditions. However, these methods usually require the participation of self-designed unsaturated compounds in the reaction. Radical tandem chemical transformations hold great potential for preparing diverse, complex, and structurally editable molecules. Radical tandem reactions can provide a way to form saturated carbon and heterocyclic compounds.

[0004] Recent reports have indicated the use of visible light photocatalysis, employing CTC strategies with inorganic and organic bases to activate compounds and generate corresponding free radicals for cyclization. However, this approach still has some unavoidable limitations, typically requiring the addition of stoichiometric or excess bases to catalyze the reaction. Other reports have proposed using photocatalysts to achieve cyclization via photo-oxidation-reduction strategies, but this requires expensive photocatalysts and specialized additives.

[0005] Current research primarily focuses on the tandem cyclization reactions of diallyl compounds. The increase in saturated C-C bonds and the editable increase in saturated cyclic alkanes are crucial in biology and medicine. It has been found that the saturation of carbon bonds in a molecule and the presence of chiral carbon atoms are closely related to clinical trials and drug development.

[0006] A rapid, molecularly editable approach to addressing this need is based on radical-based tandem cyclization reactions. These methods are powerful and versatile for constructing complex cycloalkanes and heterocycles in drug molecules and natural products. Examples include existing literature on the bifunctional cyclization of diallyl compounds reported by the Magnus Rueping group, the asymmetric sulfonation of alkenes using a photo / nickel co-catalyzed three-component system catalyzed by hydroxyl groups, the visible-light-catalyzed self-cyclization of diallyl compounds reported by the N. Gabriel Lemcof group, and a method for bifunctionalizing alkenes using oxime esters.

[0007] However, the aforementioned literature all used diallyl compounds with a carbon atom as the central atom for the reaction, generating corresponding five-membered ring compounds, but not six-membered ring compounds. According to theoretical calculations by Rene M. Koenigs, in the diallyl radical tandem cyclization process, when the central atom is a carbon atom, the energy required to generate a five-membered ring product is lower than that required to generate a six-membered ring product. Furthermore, the radical tandem cyclization reaction is very rapid, so diallyl compounds with a carbon atom as the central atom tend to generate five-membered ring products. Therefore, current cyclization reactions of diallyl compounds do not easily generate six-membered ring compounds.

[0008] However, six-membered ring compounds containing silicon atoms are widely found in various fields such as biomedicine, functional materials, and organocatalysis. In other words, although the formation of six-membered ring products presents technical challenges, they have a broad range of applications. Therefore, researching and developing a method for the tandem cyclization of diallyl compounds to generate six-membered ring products is of great significance.

[0009] In view of this, the present invention proposes a novel tandem cyclization reaction for diallyl compounds. This method, based on visible light conditions, can synthesize five-membered and six-membered cyclic compounds, providing a new approach to bifunctional cyclization. Summary of the Invention

[0010] The purpose of this invention is to provide a photocatalytic tandem cyclization reaction of diallyl compounds. This method, induced by visible light, completes a cyclization reaction without the participation of photocatalysts and additives, generating free radical intermediates with different activities in a mild manner, and establishing a new strategy for efficient, simple, and environmentally friendly bifunctionalization and cyclization.

[0011] To achieve the above objectives, the technical solution adopted is as follows:

[0012] A photocatalytic tandem cyclization reaction of diallyl compounds is as follows:

[0013] The diallyl compound and the thiosulfonate compound were mixed in a solvent and reacted under visible light irradiation and room temperature conditions with stirring to obtain the bifunctionalized cyclized product.

[0014] The diallyl compound is diethyl diallyl malonate or diallyl diphenylsilane.

[0015] Furthermore, the general reaction formula for the tandem cyclization reaction is:

[0016]

[0017] Furthermore, the aforementioned R 1 It is phenyl;

[0018] The Ar 1 Ar 2 It is one of naphthyl, phenyl, substituted phenyl, thiophene, or substituted thiazole.

[0019] Furthermore, the substituent in the substituted phenyl group is one of alkyl, halogen, alkoxy, or acyloxy groups;

[0020] The thiosulfonate compound is benzothiazole.

[0021] Furthermore, the substituents in the substituted phenyl group described above are one of C1-C4 alkyl, iodine, methoxy, and formyloxy groups.

[0022] Furthermore, the solvent is acetonitrile;

[0023] The reaction is carried out in an inert gas atmosphere.

[0024] Furthermore, the molar ratio of the thiosulfonate compound to the diallyl compound is 1.5-2.5:1;

[0025] The reaction time is 2-5 hours;

[0026] The wavelength of the visible light is 450-460nm.

[0027] Furthermore, the molar ratio of the thiosulfonate compound and the diallyl compound is 2:1.

[0028] The wavelength of the visible light is 456 nm.

[0029] Another objective of this invention is to provide a bifunctionalized cyclized product obtained by the above-described tandem cyclization reaction.

[0030] Another objective of this invention is to provide the application of the above-mentioned bifunctional cyclized products in drug synthesis, materials, and catalysts.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] 1. The technical solution of this invention, based on diallyl compounds, completes a bifunctional cyclization reaction without the participation of photocatalysts and additives through visible light induction, generating free radical intermediates with different activities in a mild manner, thus establishing a new efficient, simple, and environmentally friendly cyclization strategy for heteroatom-containing bifunctional compounds.

[0033] 2. The technical solution of this invention can complete the cyclization of five-membered and six-membered heterocycles by using different diallyl compounds, realize the regioselective functionalization reaction, greatly reduce the generation of by-products, and thus improve the yield of the target product; by using a wide range of thiosulfonates as bifunctional reagents, the scalability is increased, and a new method is provided for generating heteroatom cyclic compounds. Attached Figure Description

[0034] Figure 1 The photon spectrum is a hydrogen spectrum of the cyclic compound 1,1-diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane prepared in Example 1.

[0035] Figure 2 The carbon spectrum of the cyclic compound 1,1-diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane prepared in Example 1 is shown.

[0036] Figure 3 The image shows the two-dimensional nuclear magnetic resonance spectrum of the cyclic compound 1,1-diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane obtained in Example 1. Detailed Implementation

[0037] To further illustrate the photocatalytic tandem cyclization reaction of diallyl compounds according to the present invention and to achieve the intended purpose of the invention, the following detailed description, in conjunction with preferred embodiments, details the specific implementation methods, structures, features, and effects of the photocatalytic tandem cyclization reaction of diallyl compounds proposed according to the present invention. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable manner.

[0038] Before detailing the photocatalytic tandem cyclization reaction of diallyl compounds according to the present invention, it is necessary to further explain the relevant background mentioned in the present invention in order to achieve better results.

[0039] A rapid, molecularly editable approach to addressing this need is based on radical-based tandem cyclization reactions. This type of method is a powerful and versatile approach for constructing complex cycloalkanes and heterocycles in drug molecules and natural products. For example, Tomooka's group discovered that a stereosilane-cyclopentane polymer binds significantly to the serotonin receptor, while polymers with the opposite configuration do not. The bioactivity of chiral silicon molecules is shown below:

[0040]

[0041] In 2019, Magnus Rueping's group reported a bifunctional cyclization reaction of diallyl compounds. This three-component reaction, using a photocatalyst and a nickel catalyst as coupling agents, synthesized disubstituted cyclopentanes through the cyclization of diallyl compounds. This unprecedented catalytic process, employing synergistic catalysis of a photocatalyst and a nickel catalyst to achieve bifunctional cyclization, exhibits good atom economy and substrate applicability. The reaction equation for the photocatalytic three-component cyclization reaction of diethyl diallyl malonate is shown below:

[0042]

[0043] In 2023, Nevado's group reported a photo / nickel co-catalyzed three-component reaction for the asymmetric sulfonation of olefins. Utilizing a mild photocatalytic / nickel catalyst co-catalysis, and leveraging readily available and inexpensive starting materials, they constructed sulfonated products with high efficiency and excellent enantioselectivity, demonstrating superior functional group tolerance. The reaction formula for the photo / nickel co-catalyzed bifunctionalization of diallyl compounds is shown below:

[0044]

[0045] In 2024, N. Gabriel Lemcof's research group reported the visible-light catalytic self-cyclization reaction of diallyl compounds using a ruthenium metal catalyst. They developed an auxiliary ligand for phosphorous acid to introduce into the catalyst, allowing for catalyst regeneration via light or heat as needed, restoring catalytic activity. They also discovered that photocatalysis can be used to catalyze the self-polymerization of diallyl compounds to produce polymers. The visible-light / ruthenium-catalyzed diallyl self-cyclization reaction is shown below:

[0046]

[0047] In 2022, Molander's group reported a method for bifunctionalizing alkenes using oxime esters. Oxime esters are excellent bifunctionalizing agents. Using benzophenone as a photocatalyst, the nitrogen-oxygen bonds of the oxime ester are homolytically cleaved, followed by decarboxylation to yield alkyl and imine radicals. This method is widely applicable and yields excellent results for bifunctionalizing alkenes. The reaction formula for the energy transfer bifunctionalization of diallyl compounds using oxime esters is shown below:

[0048]

[0049] In 2023, Glorius's group reported a bifunctionalization reaction using sulfonyl oxime esters to break the N / S bond and react with alkenes. While the introduction of a sulfonyl group via the SuFEx reaction is limited, energy transfer from the sulfonyl oxime ester under visible light leads to hydrogenation addition, yielding the product. The reaction formula for the energy transfer of sulfonyl oxime esters to introduce sulfonyl fluoride is shown below:

[0050]

[0051] The above-mentioned literature all used diallyl compounds with a C atom as the central atom for the reaction, generating corresponding five-membered cyclic compounds, but no six-membered cyclic compounds were generated.

[0052] According to theoretical calculations by Rene M. Koenigs, in the tandem cyclization of diallyl radicals, when the central atom is a carbon atom, the energy required to form a five-membered ring is lower than that required to form a six-membered ring. Furthermore, the tandem cyclization reaction is very rapid, so diallyl compounds with a carbon atom as the central atom tend to form five-membered cyclized products. Therefore, current cyclization reactions of diallyl compounds do not easily produce six-membered cyclized compounds; that is, there are technical difficulties in forming six-membered cyclized compounds.

[0053] However, six-membered cyclic compounds containing silicon atoms are widely found in various fields such as biomedicine, functional materials, and organocatalysis. For example, William F. DeGrado's research group found that replacing the central spiro atom of an Amanradine analog with a silicon atom significantly improved its antiviral activity against WT A / M2 and A / M2-V27A. The antiviral activity of the silicon-substituted Amanradine analog is shown below:

[0054]

[0055] Other applications are shown in Table 1:

[0056] Table 1 Applications of organosilicon compounds

[0057]

[0058] Therefore, although the formation of six-membered ring products presents technical challenges, it also has a wide range of applications. Thus, researching and developing a method for the tandem cyclization of diallyl compounds to generate six-membered ring products is of great significance.

[0059] Having understood the relevant background mentioned in this invention, the following will provide a more detailed description of a photocatalytic tandem cyclization reaction of diallyl compounds according to the present invention, in conjunction with specific embodiments:

[0060] This invention belongs to the field of organic synthesis technology and is a method for one-step construction of cyclized products based on visible light photocatalysis. The method includes: using blue light as a light source, mixing a thiosulfonate compound and a diallyl compound in a solvent, and reacting with stirring at room temperature to obtain a bifunctionalized, cyclized product. The technical solution of this invention is as follows:

[0061] A photocatalytic tandem cyclization reaction of diallyl compounds is as follows:

[0062] The diallyl compound and the thiosulfonate compound were mixed in a solvent and reacted under visible light irradiation and room temperature conditions with stirring to obtain the bifunctionalized cyclized product.

[0063] The diallyl compound is diethyl diallyl malonate or diallyl diphenylsilane.

[0064] In the above-mentioned technical solution, the present invention combines the characteristics of silicon atoms and the properties of carbon-silicon bonds, replaces the central carbon atom of the diallyl compound with a silicon atom, changes its cyclization characteristics, and makes the energy of generating a six-membered ring product lower than that of generating a five-membered ring product, thereby overcoming the energy barrier and generating a bifunctionalized six-membered cyclized product, providing a new green method for the fields of biomedicine and materials development.

[0065] The above technical solution includes a step of purifying the obtained product after the reaction is completed.

[0066] Preferably, the general reaction formula for the tandem cyclization reaction is:

[0067]

[0068] More preferably, the R 1 It is phenyl;

[0069] The Ar 1 Ar 2 It is one of naphthyl, phenyl, substituted phenyl, thiophene, or substituted thiazole.

[0070] More preferably, the substituent in the substituted phenyl group is one of alkyl, halogen, alkoxy, and acyloxy groups;

[0071] The substituent in the substituted thiazole is phenyl.

[0072] More preferably, the substituent in the substituted phenyl group is one of C1-C4 alkyl, iodine, methoxy, and formyloxy.

[0073] Preferably, the solvent is acetonitrile (MeCN);

[0074] The reaction is carried out in an inert gas atmosphere.

[0075] Preferably, the molar ratio of the thiosulfonate compound to the diallyl compound is 1.5-2.5:1;

[0076] The reaction time is 2-5 hours;

[0077] The wavelength of the visible light is 450-460nm.

[0078] More preferably, the molar ratio of the thiosulfonate compound to the diallyl compound is 2:1.

[0079] The wavelength of the visible light is 456 nm.

[0080] A bifunctionalized cyclized product, obtained by the above-described tandem cyclization reaction, has the following structural formula:

[0081]

[0082] The above-mentioned bifunctional cyclized products have applications in drug synthesis, materials, and catalysts.

[0083] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0084] Example 1: 1,1-Diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane

[0085] The reaction formula is shown below:

[0086]

[0087] The specific synthesis steps of 1,1-diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane in this embodiment are as follows:

[0088] S-phenylbenzenesulfonyl sulfate (0.4 mmol, 0.100132 g) was loaded into a 10 mL quartz reaction tube with a branch end. Under argon protection, diallyl diphenylsilane (0.2 mmol, 0.0528 g) and solvent (2 mL) were added. The mixture was stirred for 5 h at room temperature under a 456 nm light source. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to give the final product 1,1-diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane (94.8 mg), with a yield of 92%.

[0089] The NMR spectrum of 1,1-diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane is shown below. Figure 1-2 As shown. The NMR data is: 1,1-Diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane: 1 H NMR(400MHz,Chloroform-d)δ7.73(d,J=7.8Hz,2H),7.57–7.50(m,1H),7.47(d,J =6.4Hz,2H),7.44–7.31(m,5H),7.30–7.12(m,10H),3.21(t,J=12.6Hz,1H),3.00 (d,J=5.4Hz,2H),2.27–2.12(m,1H),2.04(d,J=11.8Hz,1H),1.75(dd,J=20.2,15 .2Hz,2H),1.25(q,J=12.2Hz,1H),1.01(t,J=13.8Hz,1H),0.76(t,J=13.8Hz,1H). 13 C NMR(100MHz,Chloroform-d)δ140.06,135.15,134.61,134.46,134.26,133.62,132.97,132.31,129.9 8,129.84,129.34,128.96,128.47,128.04,127.77,127.17,65.30,44.44,42.81,31.59,18.66,18.12.

[0090] The two-dimensional NMR spectrum of 1,1-diphenyl-3-((phenylsulfonyl)methyl)-5-(phenylthio)silane is shown below. Figure 3 As shown, the product is a six-membered ring product.

[0091] Example 2: 3-((naphthalene-1-ylsulfonyl)methyl)-5-(naphthalene-1-thio)-1,1-diphenylsilane

[0092] The reaction formula is shown below:

[0093]

[0094] The specific synthesis steps are as follows:

[0095] S-(naphthyl-1-)naphthalene-1-sulfonyl sulfate (0.4 mmol, 0.14018 g) was loaded into a 10 mL quartz reaction tube with a branch end. Under argon protection, diallyl diphenylsilane (0.2 mmol, 0.0528 g) and solvent (2 mL) were added. The mixture was stirred for 5 h at room temperature and a light source at 456 nm. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to give the final product 3-((naphthyl-1-ylsulfonyl)methyl)-5-(naphthyl-1-thio)-1,1-diphenylsilane (73.8 mg), with a yield of 60%.

[0096] 3-((naphthyl-1-ylsulfonyl)methyl)-5-(naphthyl-1-thio)-1,1-diphenylsilane: 1 H NMR(400MHz,Chloroform-d)δ8.54(d,J=8.6Hz,1H),8.38–8.29(m,1H),8.00(dd,J=7.4,1.3Hz,1H),7.96(d, J=8.2Hz,1H),7.89–7.83(m,1H),7.83–7.75(m,1H),7.71(d,J=8.0Hz,1H),7.60–7.51(m,2H),7.51–7.46(m,1 H),7.46–7.41(m,2H),7.37–7.15(m,12H),3.32–3.22(m,1H),3.22–3.11(m,2H),2.14(d,J=6.8Hz,1H),2.02( dt,J=13.0,2.4Hz,1H),1.67(t,J=13.2Hz,2H),1.36–1.23(m,1H),1.02(t,J=13.8Hz,1H),0.81–0.69(m,1H). 13C NMR(100MHz,Chloroform-d)δ134.10,133.99,133.43,133.21,133.17,133.10,133.05,131.72,131.01,130.66,129.14,128.79,128.72,128.27 ,127.67,127.64,127.53,127.43,127.31,126.92,125.95,125.48,125. 14,124.70,124.47,123.30,122.89,63.94,43.79,41.71,30.63,17.23.

[0097] Example 3: 1,1-Diphenyl-3-((thiophen-2-ylsulfonyl)methyl)-5-(thiophen-2-ylthio)silane

[0098] The reaction formula is shown below:

[0099]

[0100] The specific synthesis steps are as follows:

[0101] S-(thiophen-2-yl)thiophen-2-sulfonyl sulfate (0.4 mmol, 0.0524 g) was loaded into a 10 mL quartz reaction tube with a branch end. Under argon protection, diallyl diphenylsilane (0.2 mmol, 0.1056 g) and solvent (2 mL) were added. The mixture was stirred for 5 h at room temperature and a light source at 456 nm. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to give the final product 1,1-diphenyl-3-((thiophen-2-ylsulfonyl)methyl)-5-(thiophen-2-ylthio)silane (64.2 mg), yield 61%.

[0102] 1,1-Diphenyl-3-((thiophen-2-ylsulfonyl)methyl)-5-(thiophen-2-ylthio)silane: 1H NMR(400MHz,Chloroform-d)δ7.57(dd,J=5.0,1.3Hz,1H),7.52–7.42(m,3H),7.38–7.25( m,7H),7.25–7.19(m,2H),7.08–6.98(m,2H),6.93(dd,J=5.4,3.5Hz,1H),3.14(d,J=5.8H z,2H),3.01(ddt,J=13.6,11.8,2.9Hz,1H),2.25–2.14(m,1H),2.10(dt,J=13.0,2.4Hz,1 H),1.81–1.64(m,2H),1.33–1.21(m,1H),1.00(t,J=13.8Hz,1H),0.73(d,J=13.0Hz,1H). 13 C NMR(100MHz,Chloroform-d)δ140.04,134.60,134.02,133.58,133.20,132.81,132.79,131.78,130.9 0,129.37,128.91,128.80,127.38,127.00,126.84,126.67,65.79,46.45,41.67,30.80,17.49,16.93.

[0103] Example 4: 3-(((4-(tert-butyl)phenyl)sulfonyl)methyl)-5-((4-(tert-butyl)phenyl)thio)-1,1-diphenylsilane

[0104] The reaction formula is shown below:

[0105]

[0106] The specific synthesis steps are as follows:

[0107] S-(4-(tert-butyl)phenyl)4-(tert-butyl)benzenesulfonylthioate (0.4 mmol, 0.1450 g) was loaded into a 10 mL quartz reaction tube with a branch end. Under argon protection, diallyl diphenylsilane (0.2 mmol, 0.0528 g) and solvent (2 mL) were added. The mixture was stirred for 5 h at room temperature and a light source at 456 nm. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to give the final product 3-(((4-(tert-butyl)phenyl)sulfonyl)methyl)-5-((4-(tert-butyl)phenyl)thio)-1,1-diphenylsilane (77.7 mg), yield 62%.

[0108] 3-(((4-(tert-butyl)phenyl)sulfonyl)methyl)-5-((4-(tert-butyl)phenyl)thio)-1,1-diphenylsilane: 1 H NMR(400MHz,Chloroform-d)δ7.66–7.60(m,2H),7.47(dd,J=7.6,1.8Hz,2H),7 .43–7.38(m,2H),7.38–7.30(m,3H),7.30–7.16(m,9H),3.22–3.10(m,1H),2.99 (d,J=6.4Hz,2H),2.24–2.11(m,1H),2.02(d,J=13.0Hz,1H),1.75(dd,J=22.8, 13.8Hz,2H),1.23(d,J=8.2Hz,19H),0.99(t,J=14.0Hz,1H),0.77–0.67(m,1H). 13 C NMR(100MHz,Chloroform-d)δ157.52,150.53,137.17,135.33,134.66,134.26,133.15,132.61,130.80,129.91, 129.79,128.41,128.02,127.67,126.32,126.01,65.42,42.95,35.27,34.60,31.61,31.33,31.12,18.74,18.03.

[0109] Example 5: 3-(((4-iodophenyl)sulfonyl)methyl)-5-((4-iodophenyl)thio)-1,1-diphenylsilane

[0110] The reaction formula is shown below:

[0111]

[0112] The specific synthesis steps are as follows:

[0113] S-(4-iodophenyl)-4-iodobenzenesulfonate (0.4 mmol, 0.2008 g) was loaded into a 10 mL quartz reaction tube with a branch end. Under argon protection, diallyl diphenylsilane (0.2 mmol, 0.0528 g) and solvent (2 mL) were added. The mixture was stirred for 5 h at room temperature and a light source at 456 nm. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to give the final product 3-(((4-iodophenyl)sulfonyl)methyl)-5-((4-iodophenyl)thio)-1,1-diphenylsilane (108.8 mg), yield 71%.

[0114] 3-(((4-iodophenyl)sulfonyl)methyl)-5-((4-iodophenyl)thio)-1,1-diphenylsilane: 1 HNMR(400MHz,Chloroform-d)δ7.77(d,J=8.4Hz,2H),7.56–7.50(m,2H),7.49–7.43(m,3H), 7.42–7.32(m,4H),7.31–7.25(m,3H),7.25–7.18(m,2H),6.99–6.92(m,2H),3.20(ddt,J=13. 8,11.6,2.8Hz,1H),3.05–2.91(m,2H),2.16(dddt,J=15.2,9.2,6.2,3.0Hz,1H),2.02(d,J=1 3.0Hz,1H),1.80–1.66(m,2H),1.30–1.19(m,1H),1.00(t,J=14.0Hz,1H),0.85–0.72(m,1H). 13 CNMR(100MHz,Chloroform-d)δ139.61,138.65,137.97,134.82,134.60,134.55,134.24 ,133.66,132.73,130.14,129.94,129.13,128.56,128.09,101.60,92.43,42.64,18.15.

[0115] Example 6: Diethyl-3-((benzenesulfonyl)methyl)-4-((phenylthio)methyl)cyclopentane-1,1-dicarboxylic acid ester

[0116] The reaction formula is shown below:

[0117]

[0118] The specific synthesis steps are as follows:

[0119] S-phenylbenzenesulfonyl sulfate (0.4 mmol, 0.100132 g) was loaded into a 10 mL quartz reaction tube with a branch end. Diethyl diallyl malonate (0.2 mmol, 0.048 g) and solvent (2 mL) were added under argon protection. The mixture was stirred for 2 h at room temperature and a light source at 456 nm. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to give the final product diethyl-3-((benzenesulfonyl)methyl)-4-((phenylthio)methyl)cyclopentane-1,1-dicarboxylic acid ester (37.4 mg), with a yield of 39%.

[0120] Diethyl-3-((benzenesulfonyl)methyl)-4-((benzenthio)methyl)cyclopentane-1,1-dicarboxylic acid ester: 1 HNMR(400MHz,Chloroform-d)δ7.95–7.88(m,2H),7.70–7.63(m,1H),7.62–7.54(m, 2H),7.32–7.23(m,4H),7.22–7.14(m,1H),4.17(p,J=7.2Hz,4H),3.25(dd,J=14.0, 4.5Hz, 1H), 3.12 (dd, J=14.0, 9.4Hz, 1H), 2.89 (dd, J=12.6, 6.4Hz, 1H), 2.73 (dd, J= 12.6,8.8Hz,1H),2.65–2.57(m,1H),2.56–2.25(m,5H),1.23(dt,J=8.0,7.0Hz,6H). 13 C NMR (100MHz, Chloroform-d): δ172.3,171.9,144.8,136.7,136.6,131.7,130.7,13 0.0,129.8,128.1,61.8,61.7,58.5,56.0,41.4,38.1,38.0,36.4,34.9,21.6,21.0.

[0121] Example 7: 3-((4-methoxyphenyl)thio)-1,1-diphenyl-5-(p-toluenesulfonylmethyl)silane

[0122] The reaction formula is shown below:

[0123]

[0124] The specific synthesis steps are as follows:

[0125] S-(4-methoxyphenyl)-4-methylbenzenesulfonyl sulfate (0.4 mmol, 0.1177 g) was loaded into a 10 mL quartz reaction tube with a branch end. Under argon protection, diallyl diphenylsilane (0.2 mmol, 0.0528 g) and solvent (2 mL) were added. The mixture was stirred for 5 h at room temperature and a light source at 456 nm. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to give the final product 3-((4-methoxyphenyl)thio)-1,1-diphenyl-5-(p-toluenesulfonylmethyl)silane (109.6 mg), with a yield of 98%.

[0126] 3-((4-methoxyphenyl)thio)-1,1-diphenyl-5-(p-toluenesulfonylmethyl)silane: 1H NMR(400MHz,Chloroform-d)δ7.67(d,J=8.4Hz,2H),7.51(dd,J=7.8,1.6Hz,2H),7.46– 7.37(m,3H),7.37–7.23(m,9H),6.87–6.77(m,2H),3.79(s,3H),3.15–3.01(m,3H),2.4 2(s,3H),2.17(tdq,J=12.0,6.2,3.0Hz,1H),2.05(d,J=13.2Hz,1H),1.84(d,J=13.0Hz ,1H),1.74(d,J=15.8Hz,1H),1.33–1.21(m,1H),1.07–0.97(m,1H),0.85–0.74(m,1H). 13 C NMR(100MHz,Chloroform-d)δ159.64,144.53,137.10,135.93,135.32,134.63,134.26,133.12,129.93,1 29.86,129.77,128.37,128.00,127.82,124.31,114.47,55.36,45.57,42.86,31.60,21.66,18.68,17.98.

[0127] Example 8: 1,1-Diphenyl-3-(p-Tolylthio)-5-(Toluenesulfonylmethyl)silane

[0128] The reaction formula is shown below:

[0129]

[0130] The specific synthetic steps were as follows: S-(p-methylphenyl)4-methylbenzenesulfonyl thioester (0.4 mmol, 0.1113 g) was loaded into a 10 mL quartz reaction tube with a branch end. Diallyl diphenylsilane (0.2 mmol, 0.0528 g) and solvent (2 mL) were added under argon protection. The mixture was stirred for 5 h at room temperature and a light source at a wavelength of 456 nm. After the reaction was completed, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel rapid chromatography (petroleum ether / ethyl acetate = 10:1) to obtain the final product 1,1-diphenyl-3-(p-tolylthio)-5-(toluenesulfonylmethyl)silane (90.1 mg), with a yield of 83%.

[0131] 1,1-Diphenyl-3-(p-Tolylthio)-5-(Toluenesulfonylmethyl)silane: 1H NMR(400MHz,Chloroform-d)δ7.71–7.65(m,2H),7.56–7.50(m,2H),7.48–7.37(m,3H),7.37–7.30(m,3H),7 .31–7.20(m,6H),7.09(d,J=8.0Hz,2H),3.20(ddt,J=13.6,11.8,3.0Hz,1H),3.05(d,J=6.6Hz,2H),2.43(s ,3H),2.33(s,3H),2.20(dddq,J=15.0,9.2,5.8,2.8Hz,1H),2.08(dt,J=13.0,2.4Hz,1H),1.91–1.81(m,1H ),1.78(ddt,J=14.2,3.4,1.8Hz,1H),1.34–1.24(m,1H),1.10–1.00(m,1H),0.80(dd,J=14.6,13.0Hz,1H). 13 C NMR(100MHz,Chloroform-d)δ144.52,137.40,137.13,135.27,134.64,134.25,133.08,130.50,12 9.92,129.89,129.77,129.70,128.38,128.00,127.82,65.42,44.77,31.62,21.16,18.68,18.02.

[0132] Example 9: Methyl-2-((1,1-diphenyl-5-(toluenesulfonylmethyl)silane-3-yl)thio)benzoate

[0133] The reaction formula is shown below:

[0134]

[0135] The specific synthesis steps are as follows:

[0136] Methyl 2-(p-toluenesulfonylthio)benzoate (0.4 mmol, 0.1289 g) was loaded into a 10 mL quartz reaction tube with a branch end. Under argon protection, diallyl diphenylsilane (0.2 mmol, 0.0528 g) and solvent (2 mL) were added. The mixture was stirred for 5 h at room temperature and a light source at 456 nm. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to give the final product methyl-2-((1,1-diphenyl-5-(toluenesulfonylmethyl)silane-3-yl)thio)benzoate (98.7 mg), with a yield of 85%.

[0137] Methyl-2-((1,1-diphenyl-5-(toluenesulfonylmethyl)silane-3-yl)thio)benzoate: 1 HNMR(400MHz,Chloroform-d)δ7.88(dd,J=7.8,1.6Hz,1H),7.74–7.68(m,2H),7.66–7.58(m,2H),7.52–7 .42(m,3H),7.42–7.32(m,4H),7.32–7.26(m,4H),7.18(ddd,J=15.0,7.8,1.0Hz,2H),3.87(s,3H),3.44(d dt,J=14.0,11.6,2.8Hz,1H),3.08(dd,J=6.0,1.6Hz,2H),2.43(s,4H),2.24(dt,J=13.4,2.4Hz,1H),1.85 (dq,J=14.4,2.2Hz,2H),1.36(dt,J=13.4,11.8Hz,1H),1.25–1.15(m,1H),0.86(dd,J=14.8,13.0Hz,1H). 13 C NMR(100MHz,Chloroform-d)δ167.09,144.56,139.40,137.29,135.07,134.66,134.24,132.98,132.17,131.14,130.05,1 29.96,129.86,129.34,128.49,128.06,127.99,127.75,124.61,65.37,52.12,42.35,41.82,31.59,21.65,18.41,18.04.

[0138] Example 10: 2-((1,1-diphenyl-5-(toluenesulfonylmethyl)silane-3-yl)thio)benzo[d]thiazole

[0139] The reaction formula is shown below:

[0140]

[0141] The specific synthesis steps are as follows:

[0142] S-(benzo[d]thiazol-2-yl)4-methylbenzenesulfonylthiool (0.4 mmol, 0.1285 g) was loaded into a 10 mL quartz reaction tube with a branch end. Under argon protection, diallyl diphenylsilane (0.2 mmol, 0.0528 g) and solvent (2 mL) were added. The mixture was stirred for 5 h at room temperature and a light source at 456 nm. After the reaction was complete, the solvent was removed under reduced pressure. Finally, the crude product was purified by silica gel chromatography (petroleum ether / ethyl acetate = 10:1) to obtain the final product 2-((1,1-diphenyl-5-(toluenesulfonylmethyl)silane-3-yl)thio)benzo[d]thiazol (106.6 mg), yield 91%.

[0143] 2-((1,1-diphenyl-5-(toluenesulfonylmethyl)silane-3-yl)thio)benzo[d]thiazole: 1 H NMR(400MHz,Chloroform-d)δ7.88(d,J=8.2Hz,1H),7.79–7.68(m,5H),7.55–7.45(m,3H),7.4 3(dd,J=7.2,1.2Hz,1H),7.41–7.34(m,3H),7.34–7.27(m,3H),7.27–7.23(m,2H),4.15–4.00( m,1H),3.22–3.05(m,2H),2.47–2.27(m,5H),2.17(ddt,J=14.0,3.4,1.8Hz,1H),1.90(dq,J=1 4.8, 2.4Hz, 1H), 1.53 (q, J = 12.2Hz, 1H), 1.28 (t, J = 13.8Hz, 2H), 0.92 (dd, J = 14.6, 13.0Hz, 1H). 13 C NMR(101MHz,Chloroform-d)δ165.68,153.19,136.86,135.30,134.91,134.88,134.24,132.66,130.05,129.9 3,129.90,128.44,128.06,127.89,126.09,124.42,121.61,121.03,65.30,45.99,42.51,31.77,21.65,19.33.

[0144] Example 11.

[0145] The operating steps of Example 11 are the same as those of Example 1, except for the molar ratio of S-phenylbenzenesulfonyl sulfate and diallyl diphenylsilane, as well as the wavelength and reaction time. See Table 2 for details.

[0146] Table 2

[0147]

[0148] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A tandem cyclization reaction of photocatalytic diallyl-based compounds, characterized in that, The tandem cyclization reaction is as follows: The dienyl compound and the thiosulfonate compound are mixed in a solvent, and then the reaction is stirred under visible light irradiation and at room temperature to obtain a bifunctional cyclization product; The dienyl compound is dienyl malonic acid diethyl ester or dienyl diphenyl silane.

2. The tandem cyclization reaction according to claim 1, wherein, The reaction formula of the tandem cyclization reaction is as follows:

3. The tandem cyclization reaction according to claim 2, wherein, The R mentioned 1 It is phenyl; Ar 1 , Ar 2 is one of naphthyl, phenyl, substituted phenyl, thiazole, substituted thiazole.

4. The tandem cyclization reaction according to claim 3, wherein, The substituent group in the substituted phenyl group is one of an alkyl group, a halogen, an alkoxy group and an acyloxy group; The thiosulfonate compound is benzothiazole.

5. The tandem cyclization reaction according to claim 4, wherein, The substituent group in the substituted phenyl group is one of a C1-C4 alkyl group, iodine, a methoxy group and a formyloxy group.

6. The tandem cyclization reaction according to claim 1, wherein, The solvent is acetonitrile; The reaction is carried out under an inert gas atmosphere.

7. The tandem cyclization reaction according to claim 1, wherein, The molar ratio of the thiosulfonate compound to the dienyl compound is 1.5-2.5:1; The reaction time is 2-5 hours; The wavelength of the visible light is 450-460 nm.

8. The tandem cyclization reaction according to claim 7, wherein, The molar ratio of the thiosulfonate compound to the dienyl compound is 2:

1. The wavelength of the visible light is 456 nm.

9. A bifunctional cyclized product, characterized in that, The bifunctional cyclization product obtained by the tandem cyclization reaction according to any one of claims 1-8 has the following structural formula:

10. The bifunctional cyclization product according to claim 9 is used in the synthesis of drugs, materials and catalysts.

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