Synthesis method of ester-substituted dibenzothiaza derivatives

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of ester-substituted dibenzothiaza derivatives. The invention discloses a method for realizing intramolecular series aryl carboxylation cyclization reaction of an N-(2-ethynyl aryl)-N-alkyl benzene sulfonamide compound under visible light conditions by taking the N-(2-ethynyl aryl)-N-alkyl benzene sulfonamide compound as a substrate, sodium formate as a C1 source and alkali as an additive in the atmosphere of carbon dioxide (air exists and oxygen accounts for 21%). According to the reaction, under the conditions of room temperature and visible light, the ester-substituted dibenzothiaza derivative is synthesized at a medium yield. The method has the advantages of mild reaction conditions, good substrate compatibility, simple operation, cheap and easily available raw materials, simple preparation, stable structure and the like.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for synthesizing ester-substituted dibenzothiocyanate derivatives. Background Technology

[0002] Benzo[acrylonitrile] backbone is composed of a benzene ring and a seven-membered nitrogen heterocycle, representing an important class of nitrogen-containing heterocyclic structural units widely found in many natural products and commercially available drug molecules. For example, benazepril inhibits angiotensin-converting enzyme and is used to treat hypertension and heart failure. Epinastine is a potent histamine H1 receptor antagonist used to treat inflammation caused by allergies; tianeptine is a medication for treating mental disorders and has good antidepressant effects.

[0003] Due to their unique structural features and broad biological significance, the construction of such frameworks has attracted considerable attention. Traditionally, the synthesis of these skeletal compounds typically employs Lewis acid-promoted Friedel-Crafts cyclization reactions or transition metal-catalyzed Heck-like coupling reactions. However, these reactions often require strongly acidic or high-temperature environments, limiting their potential for large-scale application. In recent years, thanks to the rapid development of radical chemistry, the use of radical-mediated tandem cyclization strategies has become a popular research area. This strategy allows for the efficient synthesis of complex heterocyclic compounds in a single step using green, mild catalytic systems with excellent atom economy, solving several problems inherent in traditional methods. Consequently, in the past few years, numerous research groups both domestically and internationally have utilized radical tandem cyclization strategies to achieve the synthesis of many distinctive benzo[a]axephin skeleton derivatives. Furthermore, carboxylic acid esters are important structural units widely found in bioactive compounds, natural products, agrochemicals, fragrances, and flavorings. In medicinal chemistry, they also serve as universal prodrug carriers for carboxyl and hydroxyl groups. Currently, there are no relevant synthetic methods for ester-substituted dibenzothiozaza derivatives, and ester-containing compounds can improve the modification and transformation of the dibenzothiozaza drug skeleton.

[0004] Therefore, there is an urgent need to develop a synthetic method for ester-substituted dibenzothiocyanate derivatives that is readily available, easy to operate, has mild reaction conditions, and is environmentally friendly. This is a technical problem that needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, the present invention discloses a method for synthesizing ester-substituted dibenzothiocyanate derivatives, which is a method that uses readily available raw materials, is simple to operate, operates under mild reaction conditions, is environmentally friendly, and is inexpensive and readily available. N-(2-ethynylaryl)- N Using alkylbenzene sulfonamides as substrates, DBACO as a base, sodium formate as the C1 source, and dimethyl sulfoxide as a solvent, an intramolecular tandem aryl carboxylation cyclization reaction was carried out to prepare ester-substituted dibenzothiozaza derivatives.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] The first technical objective of this invention is to provide a method for synthesizing ester-substituted dibenzothiocyanate derivatives, comprising the following steps: Under visible light conditions, N -(2-ethynylaryl)- N - Alkylbenzene sulfonamide compounds (Ⅰ) undergo intramolecular tandem aryl carboxylation cyclization at room temperature (reaction formula 1); after the reaction, the products are separated and characterized by conventional separation and purification methods to obtain the corresponding ester-substituted dibenzothiozaza derivatives (Ⅱ).

[0008]

[0009] Reaction 1 As shown in the above reaction formula, this invention discloses a method for using blue light as a light source under room temperature conditions, and... N -(2-ethynylaryl)- N - Alkylbenzene sulfonamide compounds (Ⅰ) were used as substrates to achieve visible light-induced intramolecular tandem aryl carboxylation cyclization at room temperature to generate ester-substituted dibenzothiozaza derivatives (Ⅱ).

[0010] The structure of the ester-substituted dibenzothiocyanate derivative (II) is as follows: ; The substituent R is an alkyl group having 1-4 carbon atoms; Substituent R 1 H, halogen; Substituent R 2 Alkyl groups having 1-4 carbon atoms, and cycloalkyl groups having 5-6 carbon atoms; Substituent R 3 It is one or more of H, halogen, alkyl, alkoxy, and phenyl with 1-4 carbon atoms; The halogen is one or more of F, Cl, and Br.

[0011] In this invention, the reaction is carried out under one or more of the following irradiations: 1~18 W white light (6500 K), 1~18 W violet light (400-405 nm), 1~18 W blue light (440-445 nm), 1~18 W green light (526-531 nm), and 1~18 W red light (700-705 nm), with 18 W blue light (440-445 nm) being optimal. The reaction light source is 440-445 nm blue light.

[0012] In this invention, the solvent in the reaction is dichloromethane, ethanol, ethyl acetate, acetonitrile, tetrahydrofuran, etc. N,N -Dimethylformamide, N,N -Dimethylacetamide, N One or more of methylpyrrolidone and dimethyl sulfoxide, preferably dimethyl sulfoxide, per 0.1 mmol N -(2-ethynylaryl)- N- For alkylbenzene sulfonamide compounds, add 0.5-3 mL of solvent, with the optimal solvent volume being 2 mL.

[0013] In this invention, the base in the reaction is any one or more of sodium carbonate, potassium carbonate, cesium carbonate, 1,4-diazabicyclo[2.2.2]octane (DABCO), and 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), with 1,4-diazabicyclo[2.2.2]octane (DABCO) being the preferred base. The molar concentration of the base in the solvent is 0.01-0.2 M, more preferably 0.05-0.15 M, and most preferably 0.1 M. In this invention, the formate in the reaction is any one or more of sodium formate, potassium formate, and cesium formate, with sodium formate being the preferred formate; the molar concentration of the formate in the solvent is preferably 0.5-10 M, and most preferably 5 M.

[0014] In this invention, the preferred molar ratio of CO2 (with air present, oxygen accounting for 21%) in the reaction is 1 bar.-2 bar., and the optimal molar ratio is 1 bar.

[0015] In this invention, the reaction time under a CO2 atmosphere (with air present and oxygen comprising 21%) is 18-30 hours, with an optimal reaction time of 24 hours. The reaction temperature under visible light is 25-80°C. o C, The optimal reaction temperature under visible light is 25-35°C. o C.

[0016] Specifically, N -(2-ethynylaryl)- N Synthesis of alkylbenzene sulfonamide compounds:

[0017] According to previous literature reports ( Org. Lett. On 23, 2021 (9303-9308), 2-iodoaniline derivative 1 (1.0 equiv., 20 mmol), ethynyltrimethylsilane (1.2 equiv., 2.35 g, 24 mmol), palladium catalyst (0.14 g, 0.01 equiv.), and cuprous iodide (0.11 g, 0.03 equiv.) were added to a solution of triethylamine (40 mL) in a 100 mL round-bottom flask, and the mixture was stirred under nitrogen and at room temperature for at least 12 hours. Then, water (100 mL) was added, and the mixture was extracted with dichloromethane (3 × 50 mL), and concentrated by rotary evaporation to give crude product 2. The crude product was used for the next synthesis without further purification.

[0018] Crude product 2 was dissolved in 30 mL of methanol. Potassium carbonate (1.5 equiv., 4.15 g, 30.0 mmol) was added, and the mixture was stirred at room temperature for 3 hours. Then, water (100 mL) was added, and the mixture was extracted with dichloromethane (3 × 50 mL) and concentrated by rotary evaporation. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (50 / 1, v / v) as eluent to give a pale yellow oily 2-ethynylaniline derivative 3 in 80–95% yield.

[0019] 2-Ethynylaniline derivative 3 (1.0 equiv., 10 mmol) and pyridine (1.4 equiv., 1.11 g, 14 mmol) were added to ultra-dry DCM (30 mL). Then, benzenesulfonyl chloride derivative 4 (1.2 equiv., 12 mmol) was slowly added to the solution. The mixture was then stirred overnight at room temperature, the solvent was removed directly by rotary evaporation, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20 / 1) to give 2-ethynylaniline derivative 5 as a white solid in 90–95% yield.

[0020] Under a nitrogen atmosphere, an alcohol (3.0 equiv., 15 mmol) and triphenylphosphine (1.5 equiv., 1.97 g, 7.5 mmol) were added to a solution of 2-acetylene aniline derivative 5 (1.0 equiv., 5 mmol) in toluene (15 mL). oAfter stirring at C for 5 minutes, diisopropyl azodicarbonate (DIAD) (1.5 ethyl acetate, 1.52 g, 7.5 mmol) was slowly added to the solution, and the mixture was stirred at room temperature until the starting material disappeared. The solvent was then removed directly by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20 / 1) to give a white solid. N -(2-ethynylaryl)- N - Alkylbenzene sulfonamide compound I, yield 90-99%.

[0021] Compared with the prior art, the beneficial effects of the present invention are: 1) This invention discloses a method for using green and environmentally friendly visible light conditions. N -(2-ethynylaryl)- N Using alkylbenzene sulfonamides as substrates, an intramolecular tandem aryl carboxylation cyclization reaction provides a convenient route for the synthesis of ester-substituted dibenzothiocyanate derivatives. Under a CO2 atmosphere (with air present and 21% oxygen), DABCO was used as a base, and sodium formate as the C1 source, an intramolecular tandem aryl carboxylation cyclization reaction was carried out, demonstrating a broad range of substrates.

[0022] 2) The process conditions of this invention are mild, the reaction is green and does not require transition metal catalysts, and the operation is simple; the raw materials are cheap, readily available, widely sourced, simple to prepare, and have stable structures. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0024] Figure 1 The images show the 1H NMR spectrum and 1C NMR spectrum of compound 2a synthesized in Example 1.

[0025] Figure 2 The images show the 1H NMR and 1C NMR spectra of compound 2c synthesized in Example 3.

[0026] Figure 3 The images show the 1H and 1C NMR spectra of compound 2h synthesized in Example 8.

[0027] Figure 4 The image shows the 1H NMR spectrum of compound 2j synthesized in Example 10.

[0028] Figure 5 The image shows the 1H NMR spectrum of compound 2n synthesized in Example 14.

[0029] Figure 6 The images show the 1H and 1C NMR spectra of compound 2r synthesized in Example 18.

[0030] Figure 7 The images show the 1H and 1C NMR spectra of compound 3a in the application example. Detailed Implementation

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in the embodiments of this application, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in this application is merely for describing particular implementations and is not intended to limit the scope of this disclosure.

[0033] Unless otherwise stated, the 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; other experimental methods and technical means not specifically mentioned herein refer to experimental methods and technical means commonly used by one of ordinary skill in the art.

[0034] To better illustrate the content of this application, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that this application can be implemented even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail in order to highlight the main points of this application.

[0035] Without conflict, the technical features disclosed in the embodiments of this application can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of this application.

[0036] This invention discloses a method for synthesizing ester-substituted dibenzothiocyanate derivatives.

[0037] To better understand the present invention, the following embodiments are provided for further detailed description of the present invention, but they should not be construed as limiting the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are also considered to fall within the protection scope of the present invention.

[0038] Example 1

[0039] like N Synthesis of -methacryloylbenzamide: According to previous literature reports ( Org. Lett. 2021, 23, 23, 9303-9308), in a 100 mL round-bottom flask, the compound (starting material R in Example 1) 1 Substituents are H, R 2 For methyl, R 3 2-Ethynylaniline 3 (1.0 equiv., 10 mmol) and pyridine (1.4 equiv., 1.11 g, 14 mmol) were added to ultra-dry DCM (30 mL). Then, p-Toluenesulfonyl chloride 4 (1.2 equiv., 12 mmol) was slowly added to the solution. The mixture was then stirred overnight at room temperature, the solvent was removed directly by rotary evaporation, and the solution was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20 / 1) to give the desired 2-ethynylaniline derivative 5 as a white solid in 95% yield.

[0040] Under a nitrogen atmosphere, methanol (3.0 equiv., 15 mmol) and triphenylphosphine (1.5 equiv., 1.97 g, 7.5 mmol) were added to a solution of 2-acetylene aniline derivative 5 (1.0 equiv., 5 mmol) in toluene (15 mL). o After stirring at C for 5 minutes, diisopropyl azodicarbonate (DIAD) (1.5 ethyl acetate, 1.52 g, 7.5 mmol) was slowly added to the solution, and the mixture was stirred at room temperature until the starting material disappeared. The solvent was then removed directly by rotary evaporation, and the product was purified by silica gel column chromatography (petroleum ether / ethyl acetate = 20 / 1) to give the desired product as a white solid. N -(2-ethynylaryl)- N -alkylbenzene sulfonamide compound 1a, 1a is a known compound ( Org. Lett. The yield was 99% (2021, 23, 23, 9303-9308).

[0041] Under a normal temperature and carbon dioxide atmosphere (with air present and oxygen accounting for 21%), add the following sequentially to a 10 mL quartz reaction tube equipped with a stir bar: N -(2-ethynylaryl)- N- Alkylbenzene sulfonamide compound 1a (28.5 mg, 0.1 mmol), CO2 (balloon, 1 bar), DABCO (22.4 mg, 0.2 mmol), HCOON (68.01 mg, 1.0 mmol), and 2 mL of dimethyl sulfoxide were reacted with 18 W blue light (440-445 nm) for 24 hours under stirring. Afterwards, esterification was performed by adding MeI (2.0 equiv.) and 65... o The reaction was carried out at C for 3 hours. After the reaction was completed, the product was extracted with ethyl acetate (3 × 10 mL), the organic layers were combined, dried with Na2SO4, filtered, and the volatile components were removed under reduced pressure. Then, the product was separated by silica gel column chromatography (eluent was petroleum ether / ethyl acetate, v / v = 3:1) to obtain the target product 2a.

[0042] Target product 2a was initially an unknown substance. Nuclear magnetic resonance (NMR) analysis further confirmed its identity, yielding the product parameter methyl 2-(2,6-dimethyl-5,5-dioxido-6,11-dihydrodibenzo[ ]). c,f ][1,2]thiazepin-11-yl)acetate(2a): New compound, white solid (24.15 mg, yield: 70%), mp 162-164 o C. 1 H NMR (600 MHz, CDCl3)δ 7.84 (d, J = 8.1 Hz, 1H), 7.42 (d, J = 7.7 Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H), 7.30 (d, J = 6.7 Hz, 1H), 7.24-7.20 (m, 3H), 4.67 (t, J =7.4 Hz, 1H), 3.54 (s, 3H), 3.42 (s, 3H), 3.18-3.10 (m, 1H), 2.38 (s, 3H). 13 CNMR (151 MHz, CDCl3)δ 171.95, 143.10, 139.41, 139.01, 138.59, 137.38, 131.10,130.51, 129.31, 128.94, 128.26, 128.15, 127.45, 51.86, 48.78, 41.67, 37.61,21.43. Comparative Example 1 The reaction steps and operating conditions were the same as in Example 1, except that the reaction was carried out under light-free conditions. The reaction was stopped, and the target product 2a was not obtained after the same post-treatment as described above. This indicates that the reaction cannot proceed without light.

[0043] Comparative Example 2 The reaction procedure and operating conditions were the same as in Example 1, except that the reaction was carried out in the absence of DABCO. The reaction was stopped, and the target product 2a was not obtained after the same post-treatment as described above. This indicates that a base is a necessary condition.

[0044] Comparative Example 3 The reaction steps and operating conditions were the same as in Example 1, except that N2 was used instead of CO2. The reaction was stopped, and the target product 2a (17.3 mg, 50%) was obtained after the same post-treatment as described above. This indicates that CO2 has a certain promoting effect on the reaction.

[0045] Comparative Example 4 The reaction procedure and operating conditions were the same as in Example 1, except that the reaction was carried out in the absence of the solvent dimethyl sulfoxide. The reaction was stopped, and the target product 2a was not obtained after the same post-treatment as described above. This demonstrates that the solvent dimethyl sulfoxide is a necessary condition.

[0046] Example 2

[0047] The reaction steps and operating conditions are the same as in Example 1, except that the iodine alkane added in the esterification reaction is different, and its R... 1 For H, R 2 For Me, R 3 For Me, raw material 1a is obtained, where 1a is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), yield 99%. The difference in the reaction system was that the starting material added was 1a (28.5 mg, 0.1 mmol). The reaction was stopped after 24 hours under blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to give product 2b.

[0048] Target product 2b was initially an unknown substance. Nuclear magnetic resonance (NMR) analysis further confirmed the target product, yielding the product parameter ethyl 2-(2,6-dimethyl-5,5-dioxido-6,11-dihydrodibenzo[…]. c,f][1,2]thiazepin-11-yl)acetate(2b):New compound, white solid (23.34 mg, yield: 65%), mp 128-130 o C. 1 H NMR (600 MHz, CDCl3)δ 7.84 (d, J = 7.9 Hz, 1H), 7.42 (dd, J = 7.9, 1.0Hz, 1H), 7.35 (td, J = 7.7, 1.5 Hz, 1H), 7.29 (dd, J = 7.7, 1.4 Hz, 1H), 7.24-7.20 (m, 3H), 4.65 (t, J = 7.6 Hz, 1H), 4.02-3.95 (m, 2H), 3.44 (s, 3H), 3.11(d, J = 7.7 Hz, 2H), 2.37 (s, 3H), 1.08 (t, J = 7.1 Hz, 3H). 13 C NMR (151 MHz, CDCl3)δ 171.43, 143.02, 139.42, 139.04, 138.63, 137.49, 131.06, 130.56,129.30, 128.91, 128.21, 128.12, 127.39, 60.75, 48.87, 41.86, 37.56, 21.41,14.18. Example 3

[0049] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 For H, raw material 1b is obtained, and 1b is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), yield 95%. The difference in the reaction system was that the starting material 1b (27.1 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to give product 2c.

[0050] The target product 2c was initially an unknown substance. Nuclear magnetic resonance (NMR) analysis further confirmed the target product, yielding the product parameter methyl 2-(6-methyl-5,5-dioxido-6,11-dihydrodibenzo[…]. c,f ][1,2]thiazepin-11-yl)acetate(2c):New compound, yellow solid (24.83 mg, yield: 75%), mp 135-137 o C. 1 H NMR (600 MHz, CDCl3)δ 7.97 (d, J = 8.0 Hz, 1H), 7.47-7.39 (m, 4H), 7.36(td, J = 7.7, 1.5 Hz, 1H), 7.31 (dd, J = 7.7, 1.3 Hz, 1H), 7.24 (td, J = 7.6, 1.2Hz, 1H), 4.73 (t, J = 7.5 Hz, 1H), 3.54 (s, 3H), 3.43 (s, 3H), 3.18 (dd, J =15.7, 7.4 Hz, 1H), 3.10 (dd, J = 15.6, 7.8 Hz, 1H). 13 C NMR (151 MHz, CDCl3)δ171.83, 140.31, 139.28, 138.89, 138.54, 132.43, 130.67, 130.54, 129.37,128.32, 128.25, 128.20, 127.48, 51.87, 48.79, 41.72, 37.74. Example 4

[0051] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3The reaction yielded reactant 1c, a known compound (Org. Lett. 2021, 23, 23, 9303-9308), with a yield of 98%. The reaction system differed in that reactant 1c (29.9 mg, 0.1 mmol) was added instead of substrate 1a. The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequent post-treatment yielded product 2d.

[0052] The target product 2d was initially an unknown substance. Further analysis using nuclear magnetic resonance (NMR) confirmed the target product, yielding the parameter methyl 2-(2-ethyl-6-methyl-5,5-dioxido-6,11-dihydrodibenzo[...]). c,f ][1,2]thiazepin-11-yl)acetate(2d):New compound, yellow solid (24.05 mg, yield:67%), mp 109-111 o C. 1 H NMR (600 MHz, CDCl3)δ 7.87 (d, J = 8.6 Hz, 1H), 7.42 (d, J =7.9 Hz, 1H), 7.34 (td, J = 7.7, 1.4 Hz, 1H), 7.31 (d, J = 7.7 Hz, 1H), 7.24-7.21(m, 3H), 4.68 (t, J = 7.5 Hz, 1H), 3.53 (s, 3H), 3.42 (s, 3H), 3.14 (qd, J =15.5, 7.6 Hz, 2H), 2.67 (q, J = 7.6 Hz, 2H), 1.23 (t, J = 7.6 Hz, 3H). 13 C NMR (151MHz, CDCl3)δ 171.87, 149.21, 139.37, 138.93, 138.56, 137.51, 130.50, 129.99,129.25, 128.26, 128.09, 127.74, 127.39, 51.80, 48.93, 41.69, 37.58, 28.69,15.23. Example 5

[0053] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 for i Pr obtains raw material 1d, where 1d is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), with a yield of 98%. The difference in the reaction system was that the starting material added was 1d (31.3 mg, 0.1 mmol) instead of the reaction substrate (1a). The reaction was stopped after 24 hours under blue light (440-445 nm) irradiation. Afterwards, the reaction was esterified to give product 2e.

[0054] The target product 2e was initially an unknown substance. Nuclear magnetic resonance (NMR) analysis further confirmed its identity. The obtained product parameter was methyl 2-(2-isopropyl-6-methyl-5,5-dioxido-6,11-dihydrodibenzo[...]. c,f ][1,2]thiazepin-11-yl)acetate(2e):New compound, yellow solid (23.87 mg, yield:64%), mp 125-127 o C. 1 H NMR (600 MHz, CDCl3)δ 7.89 (d, J = 8.1 Hz, 1H), 7.44 (d, J =7.6 Hz, 1H), 7.38-7.35 (m, 1H), 7.34-7.33 (m, 1H), 7.28 (d, J = 8.1 Hz, 1H),7.26-7.24 (m, 2H), 4.70 (t, J = 7.5 Hz, 1H), 3.55 (s, 3H), 3.44 (s, 3H), 3.16(qd, J = 15.5, 7.7 Hz, 2H), 2.95 (dt, J = 13.8, 6.9 Hz, 1H), 1.26 (dd, J = 6.9, 2.2Hz, 3H), 1.26 (d, J = 2.2 Hz, 3H). 13C NMR (151 MHz, CDCl3)δ 171.88, 153.78,139.38, 138.93, 138.52, 137.63, 130.57, 129.27, 128.73, 128.26, 128.10,127.40, 126.36, 51.80, 49.12, 41.76, 37.59, 34.11, 23.69, 22.15, 22.07. Example 6

[0055] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 for t Bu obtains raw material 1e, where 1e is a known substance ( Org. Lett. 2021, 23, 23, 9303-9308), with a yield of 99%. The difference in the reaction system was that the starting material added was 1e (32.7 mg, 0.1 mmol) instead of the reaction substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Afterwards, the reaction was esterified to obtain product 2f.

[0056] The target product 2f was initially an unknown substance. Further analysis using nuclear magnetic resonance (NMR) confirmed the target product, yielding the product parameters methyl 2-(2-(tert-butyl)-6-methyl-5,5-dioxido-6,11-dihydrodibenzo[ ] c,f ][1,2]thiazepin-11-yl)acetate (2f):New compound, yellow solid (32.12 mg, yield:83%), mp 170-172 o C. 1 H NMR (600 MHz, CDCl3)δ 7.88 (d, J = 8.3 Hz, 1H), 7.43-7.39(m, 3H), 7.36-7.33 (m, 2H), 7.24 (td, J = 7.6, 1.2 Hz, 1H), 4.69 (t, J = 7.6 Hz,1H), 3.53 (s, 3H), 3.43 (s, 3H), 3.18 (dd, J= 15.4, 7.6 Hz, 1H), 3.11 (dd, J =15.4, 7.8 Hz, 1H), 1.32 (s, 9H). 13 C NMR (151 MHz, CDCl3)δ 171.87, 156.03,139.40, 138.94, 138.11, 137.33, 130.65, 129.28, 128.10, 127.94, 127.68,127.39, 125.37, 51.80, 49.40, 41.86, 37.59, 35.09, 31.10. Example 7

[0057] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 Ph yields raw material 1f, where 1f is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), yield 95%. The reaction system differed in that the starting material (1f, 34.7 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to give 2 g of product.

[0058] The target product, 2g, was initially an unknown substance. Further analysis using nuclear magnetic resonance (NMR) confirmed the target product, yielding the product parameter methyl 2-(6-methyl-5,5-dioxido-2-phenyl-6,11-dihydrodibenzo[…]. c,f ][1,2]thiazepin-11-yl)acetate(2g):New compound, yellow oil (17.50 mg, yield: 43%). 1 H NMR (600 MHz, CDCl3)δ 8.03 (d, J = 8.2 Hz, 1H), 7.65-7.62 (m, 2H), 7.61-7.59(m, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.45 (dd, J= 8.0, 0.9 Hz, 1H), 7.43-7.40 (m,1H), 7.38 (td, J = 7.9, 1.5 Hz, 1H), 7.35-7.34 (m, 1H), 7.28-7.25 (m, 1H), 4.81(t, J = 7.4 Hz, 1H), 3.55 (s, 3H), 3.47 (s, 3H), 3.25 (dd, J = 15.7, 7.4 Hz, 1H), 3.16 (dd, J = 15.7, 7.8 Hz, 1H). 13 C NMR (151 MHz, CDCl3)δ 171.87, 145.27,139.32, 139.13, 139.07, 138.86, 130.59, 129.42, 129.28, 129.16, 128.77,128.62, 128.27, 127.52, 127.36, 126.81, 51.92, 49.11, 41.74, 37.73. Example 8

[0059] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 1g of raw material was obtained for OMe, and 1g is a known substance ( Org. Lett. 2021, 23, 23, 9303-9308), with a yield of 95%. The reaction system differed in that 1 g (30.1 mg, 0.1 mmol) of the starting material was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to obtain the product for 2 hours.

[0060] The target product was initially unknown 2 hours after extraction. Further analysis using nuclear magnetic resonance (NMR) confirmed the target product, yielding the product parameter methyl 2-(2-methoxy-6-methyl-5,5-dioxido-6,11-dihydrodibenzo[]. c,f] [1,2]thiazepin-11-yl)acetate(2h):New compound, yellow oil (21.66 mg, yield: 60%). 1H NMR (600 MHz, CDCl3)δ 7.88 (d, J = 8.7 Hz, 1H), 7.40 (d, J = 7.8 Hz, 1H),7.34-7.32 (m, 1H), 7.28 (d, J = 7.6 Hz, 1H), 7.22 (t, J = 7.5 Hz, 1H), 6.90-6.86(m, 2H), 4.69 (t, J = 7.2 Hz, 1H), 3.83 (s, 3H), 3.55 (s, 3H), 3.39 (s, 3H), 3.20 (dd, J = 15.8, 7.3 Hz, 1H), 3.11 (dd, J = 15.8, 7.7 Hz, 1H). 13 C NMR (151 MHz, CDCl3)δ 171.87, 162.17, 140.86, 139.47, 138.77, 131.88, 130.31, 130.23,129.20, 128.03, 127.38, 115.63, 113.04, 55.68, 51.85, 48.49, 41.26, 37.52. Example 9

[0061] The reaction steps and operating conditions are the same as in Example 1, except that the aromatic amines selected for the preparation of the raw materials are different, and their R... 1 For OMe, R 2 For Me, R 3 Me obtains raw material 1h, where 1h is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), yield 96%. The reaction system differed in that 1h (31.5 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was subjected to post-esterification to obtain product 2i.

[0062] The target product 2i was initially an unknown substance. Further NMR analysis confirmed its identity, yielding the following parameters: methyl 2-(8-methoxy-2,6-dimethyl-5,5-dioxido-6,11-dihydrodibenzo[c,f][1,2]thiazepin-11-yl)acetate(2i): New compound, yellow solid (19.5 mg, yield: 52%), mp 10⁴-10⁶. o C. 1 H NMR (600 MHz, CDCl3)δ 7.82 (d, J = 8.0 Hz, 1H), 7.34 (d, J = 8.7Hz, 1H), 7.19 (d, J = 8.0 Hz, 1H), 7.18 (s, 1H), 6.85 (dd, J = 8.7, 2.8 Hz, 1H), 6.79 (d, J = 2.8 Hz, 1H), 4.59 (s, 1H), 3.77 (s, 3H), 3.57 (s, 3H), 3.40 (s,3H), 3.13 (d, J = 7.0 Hz, 2H), 2.36 (s, 3H). 13 C NMR (151 MHz, CDCl3)δ 171.86,159.01, 142.86, 140.94, 138.49, 137.61, 131.60, 130.76, 128.96, 128.87,128.35, 115.13, 114.54, 55.61, 51.88, 48.40, 41.06, 37.59, 21.37. Example 10

[0063] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 For F, raw material 1i is obtained, where 1i is a known substance ( Org. Lett.(2021, 23, 23, 9303-9308), with a yield of 96%. The reaction system differed in that the starting material (1i, 28.9 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (465 nm) irradiation. Subsequently, the reaction was esterified to give product 2j.

[0064] The target product 2j was initially an unknown substance. Further analysis using nuclear magnetic resonance (NMR) confirmed the target product, yielding the product parameter methyl 2-(2-fluoro-6-methyl-5,5-dioxido-6,11-dihydrodibenzo[] . c,f ][1,2]thiazepin-11-yl)acetate(2j):New compound, white solid (20.09 mg, yield: 55%),mp 119-121 o C. 1 H NMR (600 MHz, CDCl3)δ 7.97 (dd, J = 8.8, 5.5 Hz, 1H), 7.42 (d, J =7.6 Hz, 1H), 7.38-7.35 (m, 1H), 7.30-7.29 (m, 1H), 7.27-7.24 (m, 1H), 7.15(dd, J = 9.5, 2.4 Hz, 1H), 7.11-7.08 (m, 1H), 4.72 (t, J = 7.4 Hz, 1H), 3.57 (s,3H), 3.42 (s, 3H), 3.20 (dd, J = 15.9, 7.5 Hz, 1H), 3.09 (dd, J = 15.9, 7.5 Hz, 1H). 13 C NMR (151 MHz, CDCl3)δ 171.56, 164.13 (d, J = 255.19 Hz), 141.86 (d, J =9.06 Hz), 139.13, 138.40, 136.36 (d, J = 3.02 Hz), 130.94 (d, J = 9.06 Hz),130.31, 129.54, 128.38, 127.56, 117.35 (d, J= 22.65 Hz), 115.43 (d, J = 22.65Hz), 51.99, 48.12, 41.25, 37.74. 19 F NMR (565 MHz, CDCl3)δ -28.19. Example 11

[0065] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 For Cl, raw material 1j is obtained, where 1j is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), with a yield of 78%. The reaction system differed in that the starting material (1j, 30.5 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (465 nm) irradiation. Subsequently, the reaction was esterified to give product 2k.

[0066] The target product 2k was initially an unknown substance, but it was further confirmed by nuclear magnetic resonance (NMR) analysis. The product parameters obtained were methyl 2-(2-chloro-6-methyl-5,5-dioxido-6,11-dihydrodibenzo[] c,f ][1,2]thiazepin-11-yl)acetate(2k):New compound, yellow oil (16.43 mg, yield: 45%). 1 H NMR (600 MHz, CDCl3)δ 7.97 (d, J = 7.9 Hz, 1H), 7.44 (dq, J = 22.1, 7.4 Hz, 4H), 7.36 (t, J = 7.6 Hz, 1H), 7.31 (d, J = 7.4 Hz, 1H), 7.26-7.23 (m, 1H), 4.73(t, J = 7.5 Hz, 1H), 3.54 (s, 3H), 3.44 (s, 3H), 3.18 (dd, J = 15.7, 7.4 Hz, 1H), 3.10 (dd, J= 15.7, 7.8 Hz, 1H). 13 C NMR (151 MHz, CDCl3)δ 171.87, 140.34,139.31, 138.92, 138.57, 132.45, 130.70, 130.57, 129.40, 128.35, 128.27,128.24, 127.51, 51.90, 48.83, 41.75, 37.77. Example 12

[0067] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 Br yields raw material 1k, where 1k is a known substance ( Org. Lett. 2021, 23, 23, 9303-9308), with a yield of 95%. The reaction system differed in that 1k (34.9 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to give product 2l.

[0068] The target product 2l was initially an unknown substance. Further analysis using nuclear magnetic resonance (NMR) confirmed the target product, yielding the product parameter methyl 2-(2-bromo-6-methyl-5,5-dioxido-6,11-dihydrodibenzo[] . c,f ][1,2]thiazepin-11-yl)acetate(2l):New compound, yellow solid (18.36 mg, yield:45%), mp 140-142 o C. 1 H NMR (600 MHz, CDCl3)δ 7.97 (d, J = 8.0 Hz, 1H), 7.46-7.44(m, 1H), 7.42 (s, 1H), 7.41 (dd, J = 9.1, 1.9 Hz, 1H), 7.36 (td, J = 7.6, 1.5 Hz, 1H), 7.31 (dd, J= 7.7, 1.4 Hz, 1H), 7.26-7.23 (m, 1H), 4.73 (t, J = 7.5 Hz, 1H), 3.54 (s, 3H), 3.43 (s, 3H), 3.18 (dd, J = 15.7, 7.4 Hz, 1H), 3.10 (dd, J = 15.7, 7.8 Hz, 1H). 13 C NMR (151 MHz, CDCl3)δ 171.85, 140.32, 139.29, 138.90, 138.55,132.44, 130.69, 130.55, 129.38, 128.33, 128.26, 128.22, 127.49, 51.89, 48.81,41.73, 37.76. Example 13

[0069] The reaction steps and operating conditions are the same as in Example 1, except that the sulfonyl chlorides selected in the preparation of the raw materials are different, and their R... 1 For H, R 2 For Me, R 3 To obtain raw material 1l for meta-Br, 1l is a known substance ( Org. Lett. 2021, 23, 23, 9303-9308), with a yield of 96%. The reaction system differed in that 1 L (34.9 mg, mmol) of the starting material was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to give product 2m.

[0070] The target product 2m was initially an unknown substance, but was further confirmed as the target product by nuclear magnetic resonance (NMR) analysis. The obtained product parameters were methyl 2-(3-bromo-6-methyl-5,5-dioxido-6,11-dihydrodibenzo[] c,f ][1,2]thiazepin-11-yl)acetate(2m):New compound, yellow solid (13.06 mg, yield:32%), mp 133-135 o C. 1 H NMR (600 MHz, CDCl3)δ 7.97 (d, J= 8.0 Hz, 1H), 7.46-7.44(m, 1H), 7.42 (d, J = 7.4 Hz, 1H), 7.36 (td, J = 7.6, 1.5 Hz, 1H), 7.31 (dd, J =7.7, 1.4 Hz, 1H), 7.26-7.23 (m, 1H), 4.73 (t, J = 7.5 Hz, 1H), 3.54 (s, 3H), 3.44 (s, 3H), 3.18 (dd, J = 15.7, 7.4 Hz, 1H), 3.10 (dd, J = 15.7, 7.8 Hz, 1H). 13 CNMR (151 MHz, CDCl3)δ 171.87, 140.33, 139.30, 138.92, 138.57, 132.45, 130.70,130.57, 129.40, 128.34, 128.27, 128.23, 127.50, 51.90, 48.85, 41.74, 37.77. Example 14

[0071] The reaction steps and operating conditions are the same as in Example 1, except that the aromatic amines selected for the preparation of the raw materials are different, and their R... 1 For F, R 2 For Me, R 3 Me obtains raw material 1m, where 1m is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), yield 95%. The reaction system differed in that the starting material (1m, 30.3 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to give product 2n.

[0072] The target product 2n was initially an unknown substance, but was further confirmed as the target product by nuclear magnetic resonance (NMR) analysis. The obtained product parameters are methyl 2-(8-fluoro-2,6-dimethyl-5,5-dioxido-6,11-dihydrodibenzo[ ] c,f][1,2]thiazepin-11-yl)acetate(2n):New compound, white solid (13.07 mg, yield: 36%),mp 168-170 o C. 1 H NMR (600 MHz, CDCl3) δ 7.84 (d, J = 8.1 Hz, 1H), 7.40 (dd, J =8.7, 5.1 Hz, 1H), 7.22 (d, J = 8.2 Hz, 1H), 7.19 (s, 1H), 7.05-7.00 (m, 2H), 4.63 (t, J = 6.9 Hz, 1H), 3.58 (s, 3H), 3.40 (s, 3H), 3.13 (d, J = 7.5 Hz, 1H), 2.38 (s, 3H). 13 C NMR (151 MHz, CDCl3)δ 171.55, 161.41 (d, J = 249.15 Hz),143.17, 141.51, 137.81, 137.14, 135.20 (d, J = 3.02 Hz), 130.75, 129.32 (d, J =9.06 Hz), 129.06, 128.29, 116.87 (d, J = 18.12 Hz), 116.14 (d, J = 22.65 Hz),51.89, 48.01, 41.01, 37.66, 21.33. 19 F NMR (565 MHz, CDCl3)δ -34.93. Example 15

[0073] The reaction steps and operating conditions are the same as in Example 1, except that the aromatic amines selected for the preparation of the raw materials are different, and their R... 1 For Cl, R 2 For Me, R 3 Me obtains raw material 1n, where 1n is a known substance ( Org. Lett.2021, 23, 23, 9303-9308), with a yield of 98%. The difference in the reaction system was that the starting material (1n) (31.9 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Afterwards, the reaction was esterified to give product 2o.

[0074] The target product 2o was initially an unknown substance. Nuclear magnetic resonance (NMR) analysis further confirmed its identity. The obtained product parameter was methyl 2-(8-chloro-2,6-dimethyl-5,5-dioxido-6,11-dihydrodibenzo[...]. c,f ][1,2]thiazepin-11-yl)acetate(2o):New compound, white solid (15.16 mg, yield: 40%),mp 165-167 o C. 1 H NMR (600 MHz, CDCl3)δ 7.83 (d, J = 8.1 Hz, 1H), 7.34-7.30 (m,3H), 7.22 (d, J = 8.2 Hz, 1H), 7.20 (s, 1H), 4.63 (t, J = 7.3 Hz, 1H), 3.58 (s,3H), 3.37 (s, 3H), 3.13 (qd, J = 15.9, 7.5 Hz, 1H), 2.38 (s, 3H). 13 C NMR (151MHz, CDCl3)δ 171.67, 143.40, 140.72, 138.12, 137.84, 137.00, 133.55, 131.07,130.36, 129.36, 129.14, 128.78, 128.35, 51.99, 48.27, 41.38, 37.66, 22.09,21.43. Example 16

[0075] The reaction steps and operating conditions are the same as in Example 1, except that the aromatic amines selected for the preparation of the raw materials are different, and their R... 1 For Br, R 2 For Me, R 3 Me obtains raw material 1o, where 1o is a known substance (Org. Lett. (2021, 23, 23, 9303-9308), with a yield of 83%. The reaction system differed in that the starting material (1o, 36.3 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to give product 2p.

[0076] The target product 2p was initially an unknown substance. Nuclear magnetic resonance (NMR) analysis confirmed its identity, yielding the product parameter methyl 2-(8-bromo-2,6-dimethyl-5,5-dioxido-6,11-dihydrodibenzo[] . c,f ][1,2]thiazepin-11-yl)acetate(2p):New compound, white solid (13.54 mg, yield: 32%),mp 148-150 o C. 1 H NMR (600 MHz, CDCl3)δ 7.85 (d, J = 8.6 Hz, 1H), 7.42 (dd, J = 7.9, 1.0 Hz, 1H), 7.35 (td, J = 7.6, 1.5 Hz, 1H), 7.30 (dd, J = 7.7, 1.3 Hz, 1H),7.24-7.20 (m, 1H), 7.21 (d, J = 7.1 Hz, 1H), 4.67 (t, J = 7.4 Hz, 1H), 3.54 (s, 3H), 3.42 (s, 3H), 3.17-3.10 (m, 2H), 2.38 (s, 3H). 13 C NMR (151 MHz, CDCl3)δ171.97, 143.11, 139.42, 139.02, 138.60, 137.39, 131.10, 130.51, 129.32,128.95, 128.28, 128.16, 127.46, 51.87, 48.81, 41.67, 37.63, 22.12, 21.44. Example 17

[0077] The reaction steps and operating conditions are the same as in Example 1, except that the protecting group of N is different in the preparation of the raw materials, and its R 1 For H, R 2 For Et, R 3 Me obtains raw material 1p, where 1p is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), with a yield of 96%. The reaction system differed in that the starting material (1p, 29.9 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (465 nm) irradiation. Subsequently, the reaction was esterified to give product 2q.

[0078] The target product 2q was initially an unknown substance, but it was further confirmed by nuclear magnetic resonance (NMR) analysis. The product parameters were methyl 2-(6-ethyl-2-methyl-5,5-dioxido-6,11-dihydrodibenzo[ ]). c,f ][1,2]thiazepin-11-yl)acetate(2q):New compound, white solid (18.67 mg, yield: 52%),mp 151-153 o C. 1 H NMR (600 MHz, CDCl3) δ 7.97 (d, J = 8.0 Hz, 1H), 7.46-7.44 (m,1H), 7.42 (s, 1H), 7.41 (dd, J = 9.1, 1.9 Hz, 1H), 7.36 (td, J = 7.6, 1.5 Hz, 1H), 7.31 (dd, J = 7.7, 1.4 Hz, 1H), 7.26-7.23 (m, 1H), 4.73 (t, J = 7.5 Hz, 1H), 3.54 (s, 3H), 3.43 (s, 3H), 3.18 (dd, J = 15.7, 7.4 Hz, 1H), 3.10 (dd, J = 15.7, 7.8 Hz, 1H). 13C NMR (151 MHz, CDCl3)δ 171.92, 142.97, 140.33, 138.59, 137.95,137.68, 130.01, 129.71, 128.96, 128.81, 128.69, 128.40, 128.37, 128.33,51.90, 46.49, 45.89, 40.78, 21.47, 14.95. Example 18

[0079] The reaction steps and operating conditions are the same as in Example 1, except that the protecting group of N is different in the preparation of the raw materials, and its R 1 For H, R 2 for n Pr, R 3 Me obtains raw material 1q, where 1q is a known substance ( Org. Lett. (2021, 23, 23, 9303-9308), with a yield of 91%. The reaction system differed in that the starting material (1q, 31.3 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (465 nm) irradiation. Subsequently, the reaction was esterified to give product 2r.

[0080] The target product 2r was initially an unknown substance, but it was further confirmed by nuclear magnetic resonance (NMR) analysis. The product parameters were methyl 2-(2-methyl-5,5-dioxido-6-propyl-6,11-dihydrodibenzo[ ]). c,f ][1,2]thiazepin-11-yl)acetate(2r):New compound, white solid (18.65 mg, yield: 50%),mp 148-150 o C. 1 H NMR (600 MHz, CDCl3)δ 7.80 (d, J = 8.1 Hz, 1H), 7.39 (d, J = 7.9Hz, 1H), 7.29-7.26 (m, 1H), 7.24 (t, J = 8.4 Hz, 1H), 7.22 -7.19 (m, 1H), 7.14(d, J= 8.1 Hz, 1H), 7.11 (s, 1H), 4.87 (s, 1H), 3.75-3.67 (m, 2H), 3.55 (s,3H), 3.20- 3.12 (m, 2H), 2.33 (s, 3H), 1.70 (dtt, J = 20.7, 13.6, 6.7 Hz, 2H),0.92 (t, J = 7.4 Hz, 3H). 13 C NMR (151 MHz, CDCl3)δ 171.84, 142.89, 140.57,138.57, 137.87, 137.78, 129.43, 129.11, 129.00, 128.83, 128.75, 128.50,128.37, 52.84, 51.91, 45.81, 40.16, 22.86, 21.46, 11.38. Example 19

[0081] The reaction steps and operating conditions are the same as in Example 1, except that the protecting group of N is different in the preparation of the raw materials, and its R 1 For H, R 2 for n Bu, R 3 For Me, raw material 1r is obtained, where 1r is a known substance ( Org. Lett. 2021, 23, 23, 9303-9308), with a yield of 96%. The difference in the reaction system was that the starting material (1r, 32.7 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to give product 2s.

[0082] The target product 2S was initially an unknown substance, but was further confirmed as the target product by nuclear magnetic resonance (NMR) analysis. The obtained product parameters were methyl 2-(6-butyl-2-methyl-5,5-dioxido-6,11-dihydrodibenzo[ ]). c,f ][1,2]thiazepin-11-yl)acetate(2s):New compound, white solid (21.67 mg, yield: 56%),mp 114-116 o C. 1H NMR (600 MHz, CDCl3)δ 7.83 (d, J = 8.1 Hz, 1H), 7.43 (d, J = 7.9Hz, 1H), 7.31 (td, J = 7.6, 1.6 Hz, 1H), 7.29 (d, J = 7.7 Hz, 1H), 7.25- 7.22 (m,1H), 7.17 (d, J = 8.1 Hz, 1H), 7.14 (s, 1H), 4.88 (s, 1H), 3.79 (t, J = 7.8 Hz, 2H), 3.58 (s, 3H), 3.19 (d, J = 7.3 Hz, 2H), 2.36 (s, 3H), 1.75-1.63 (m, 2H), 1.40-1.34(m, 2H), 0.92 (t, J = 7.4 Hz, 3H). 13 C NMR (151 MHz, CDCl3)δ 171.85,142.89, 140.57, 138.60, 137.83, 129.44, 129.20, 128.93, 128.85, 128.76,128.49, 128.36, 51.90, 50.87, 45.97, 40.18, 31.62, 22.16, 22.07, 21.46,20.17, 13.79. Example 20

[0083] The reaction steps and operating conditions are the same as in Example 1, except that the protecting group of N is different in the preparation of the raw materials, and its R 1 For H, R 2 It is cyclopentyl, R 3 Me obtains raw material 1s, where 1s is a known substance ( Org. Lett. 2021, 23, 23, 9303-9308), with a yield of 89%. The difference in the reaction system was that the starting material (1s, 33.9 mg, 0.1 mmol) was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Afterwards, the reaction was esterified to give product 2t.

[0084] The target product 2t was initially an unknown substance. Nuclear magnetic resonance (NMR) analysis further confirmed the target product, and the obtained product parameters were methyl 2-(6-cyclopentyl-2-methyl-5,5-dioxido-6,11-dihydrodibenzo[…]. c,f ][1,2]thiazepin-11-yl)acetate(2t):New compound, white solid (22.34 mg, yield: 56%),mp 152-154 o C. 1 H NMR (600 MHz, CDCl3)δ 7.84 (d, J = 8.1 Hz, 1H), 7.45 (d, J = 7.2Hz, 1H), 7.29 (dd, J = 16.9, 6.9 Hz, 3H), 7.19 (d, J = 8.0 Hz, 1H), 7.14 (s, 1H), 4.91 (s, 1H), 4.54-4.51 (m, 1H), 3.60 (s, 3H), 3.19 (s, 2H), 2.37 (s, 3H), 2.18 (s, 1H), 1.84-1.55 (m, 7H). 13 C NMR (151 MHz, CDCl3)δ 171.86, 142.68,141.56, 138.52, 136.39, 132.12, 131.12, 130.77, 129.98, 129.52, 129.39,128.66, 123.54, 62.51, 51.88, 40.70, 32.01, 23.66, 22.87, 22.78, 21.46,14.21. Example 21

[0085] The reaction steps and operating conditions are the same as in Example 1, except that the protecting group of N is different in the preparation of the raw materials, and its R 1 For H, R 2 For cyclohexyl, R 3 Me obtains 1t of raw material, where 1t is a known substance ( Org. Lett.(2021, 23, 23, 9303-9308), yield 92%. The reaction system differed in that 1t (35.3 mg, 0.1 mmol) of the starting material was added instead of the substrate (1a). The reaction was stopped after 24 hours of blue light (440-445 nm) irradiation. Subsequently, the reaction was esterified to obtain product 2u.

[0086] The target product 2u was initially an unknown substance. Nuclear magnetic resonance (NMR) analysis confirmed its identity, and the product parameters were determined to be methyl 2-(6-cyclohexyl-2-methyl-5,5-dioxido-6,11-dihydrodibenzo[…]. c,f ][1,2]thiazepin-11-yl)acetate(2u):New compound, yellow oil (18.59 mg, yield: 45%). 1 H NMR (600 MHz, CDCl3)δ 7.84 (d, J = 8.0 Hz, 1H), 7.44 (s, 1H), 7.26 (d, J = 1.8Hz, 3H), 7.16 (d, J = 8.0 Hz, 1H), 7.08 (s, 1H), 5.31 (s, 1H), 4.03 (s, 1H), 3.60 (s, 3H), 3.31 (s, 1H), 3.16 (dd, J = 15.8, 7.8 Hz, 1H), 2.36 (s, 3H), 1.81(dd, J = 13.3, 2.3 Hz, 1H), 1.68-1.26 (m, 7H), 1.02-0.84 (m, 2H). 13 C NMR (151MHz, CDCl3)δ 172.04, 142.81, 141.94, 138.60, 137.69, 135.74, 131.23, 129.52,128.96, 128.56, 128.36, 128.03, 61.17, 51.92, 42.03, 39.04, 35.96, 32.02,30.76, 29.79, 26.27, 26.22, 25.43, 21.58. Application examples

[0087] First, a derivatization experiment was conducted on the target product 2a obtained in Example 1 to further demonstrate the synthetic application of this scheme. Product 2a (0.1 mmol) and MeNH2 (2 mL) were synthesized under a nitrogen atmosphere at a temperature of 60°C. o C, after reacting for 24 hours, yields the amination product 3a.

[0088] The target product was confirmed by nuclear magnetic resonance (NMR) analysis, and the product parameters were 2-(2,6-dimethyl-5,5-dioxido-6,11-dihydrodibenzo[ c,f [1,2]thiazepin-11-yl)- N -methylacetamide(3a):New compound, white solid (29.24 mg, yield: 85%), mp 163-165 o C. 1 H NMR (600MHz, CDCl3)δ 7.78 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 7.7 Hz, 1H), 7.25-7.19 (m,3H), 7.18-7.14 (m, 2H), 5.45 (s, 1H), 4.78-4.76 (m, 1H), 3.14 (s, 3H), 3.03(dd, J = 14.3, 8.7 Hz, 1H), 2.81 (dd, J = 14.3, 6.2 Hz, 1H), 2.52 (d, J = 4.8 Hz, 3H), 2.32 (s, 3H). 13 C NMR (151 MHz, CDCl3)δ 171.19, 143.63, 140.03, 138.25,137.47, 135.76, 132.48, 131.43, 128.78, 128.52, 128.50, 127.80, 127.64,49.84, 45.14, 38.96, 26.26, 21.39. Furthermore, further reference (Bioorg. Med. Chem. Lett. 2007, 17, 5465.) shows that it can be converted into the drug molecular skeleton of Tianeptine.

[0089] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for synthesizing an ester-substituted dibenzothiocyanate derivative, characterized in that, N -(2-ethynylaryl)- N Using alkylbenzene sulfonamides as substrates, ester-substituted dibenzothiocyanate derivatives were synthesized under visible light conditions in a carbon dioxide atmosphere (with air present and oxygen at 21%), with the aid of base and formate.

2. The method for synthesizing ester-substituted dibenzothiocyanate derivatives according to claim 1, characterized in that, by N -(2-ethynylaryl)- N Using alkylbenzene sulfonamides as substrates, the compounds generated by intramolecular tandem aryl carboxylation and cyclization are ester-substituted dibenzothioazene derivatives (II). The specific preparation process is as follows: Under a carbon dioxide atmosphere (with air present and oxygen accounting for 21%), ... N -(2-ethynylaryl)- N - Alkylbenzene sulfonamide compounds, when a base or formate is added to a solvent, undergo a visible light-induced reaction to generate ester-substituted dibenzothiozaza derivatives (II).

3. The method for synthesizing ester-substituted dibenzothiocyanate derivatives according to claim 1 or 2, characterized in that, N -(2-ethynylaryl)- N The structures of alkylbenzene sulfonamide compounds are as follows: ； The structures of ester-substituted dibenzothiocyanate derivatives are as follows: ； The substituent R is an alkyl group having 1-4 carbon atoms; Substituent R 1 H, halogen; Substituent R 2 Alkyl groups having 1-4 carbon atoms, and cycloalkyl groups having 5-6 carbon atoms; Substituent R 3 It is one or more of H, halogen, alkyl, alkoxy, and phenyl with 1-4 carbon atoms; The halogen is one or more of F, Cl, and Br.

4. The method for synthesizing ester-substituted dibenzothiocyanate derivatives according to claim 1 or 2, characterized in that, The visible light is one or more of the following: 1~18 W white light (6500 K), 1~18 W violet light (400-405 nm), 1~18 W blue light (440-445 nm), 1~18 W green light (526-531 nm), and 1~18 W red light (700-705 nm).

5. The method for synthesizing ester-substituted dibenzothiocyanate derivatives according to claim 2, characterized in that, The solvent is dichloromethane, ethanol, ethyl acetate, acetonitrile, tetrahydrofuran, etc. N,N -Dimethylformamide, N,N -Dimethylacetamide, N One or more of methylpyrrolidone and dimethyl sulfoxide, per 0.1 mmol N -(2-ethynylaryl)- N - For alkylbenzene sulfonamide compounds, add 0.5-3 mL of solvent.

6. The method for synthesizing ester-substituted dibenzothiocyanate derivatives according to claim 1 or 2, characterized in that, The base is any one or more of sodium carbonate, potassium carbonate, cesium carbonate, 1,4-diazabicyclo[2.2.2]octane (DABCO), and 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), and the molar concentration of the base in the solvent is 0.01-0.2M.

7. The method for synthesizing ester-substituted dibenzothiocyanate derivatives according to claim 1 or 2, characterized in that, The formate is any one or more of sodium formate, potassium formate, and cesium formate, and the molar concentration of the formate in the solvent is 0.5-10 M.

8. The method for synthesizing ester-substituted dibenzothiocyanate derivatives according to claim 1 or 2, characterized in that, The molar ratio of CO2 (containing air, with oxygen accounting for 21%) is 1 bar.-2 bar.

9. The method for synthesizing ester-substituted dibenzothiocyanate derivatives according to claim 1 or 2, characterized in that, The reaction, carried out in a CO2 atmosphere (with air present and oxygen comprising 21%), lasts for 18-30 hours at a temperature of 25-35°C. o C.

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