Sugar onium salt, synthesis method and application thereof

Abstract

This invention discloses a glycoene sulfonium salt, its synthetic method, and its applications, relating to the fields of organic synthesis and saccharide chemistry. By adding a base to suppress byproducts, this invention proposes a DHSO-Tf₂O-DTBMP system, which can efficiently synthesize monosaccharide and disaccharide glycoene sulfonium salts with different protecting groups in excellent yields of 85-99%. In the glycoene sulfonium salt, a dibenzohexane sulfonium group centered on a tetravalent thiocation is attached to the C-2 position of the glycoene unit, and the double bond of the glycoene unit is directly linked to the thiocation, forming a stable glycoene sulfonium structure. The entire synthetic reaction is simple to operate, requiring only 20 minutes, and eliminates the need for column chromatography separation and purification, saving cumbersome steps and making it suitable for large-scale synthesis.

Description

Technical Field

[0001] This invention relates to the fields of organic synthesis and saccharochemistry, specifically to a glycoene sulfonium salt, its synthesis method, and its application. Background Technology

[0002] C2-functionalized carbohydrates are widely distributed in nature, including many natural products and clinically important antiviral, anticancer, and antibiotic drugs. They also serve as important components of cell walls, glycoproteins, and glycosyltransferases in organisms. Therefore, developing a simple and universal method to obtain C2-functionalized carbohydrates from readily available starting materials is of great significance.

[0003] Currently reported modifications of the C2 functional group of glycoenes are mainly halogenation reactions. The synthesis of C2-halogenated glycoenes typically requires toxic and highly corrosive liquid bromine or thionyl chloride, has poor functional group compatibility, and is limited by substrate availability. Tetrahedron Lett 2006, 47, 8337; Bioorg. Med. Chem. 2010, 18, 3656. In 2014, Vankar developed an efficient method to synthesize 2-haloglycoene compounds such as 2-bromoglycoene and 2-iodoglycoene (…). Org. Lett. (2014, 16, 1172), this is currently the most widely used method, and various C2-sugar analogs have been prepared using this method. Although significant progress has been made, this method has certain limitations. First, the yield of 2-iodoglycoene is low, the synthesis is difficult, and it requires expensive metal reagents such as silver nitrate, making it difficult to widely apply industrially. Another method is the 1,2-radical migration reaction developed by Ngai, which uses bromoglycosides as glycosyl donors and light and excited-state palladium as catalysts, achieving 2-position modification of glycosyl groups under mild conditions. Acc. Chem. Res. .2025, 58, 1815). However, this light- and excited-state palladium-mediated radical reaction requires expensive palladium catalysts and cumbersome light reaction facilities (many laboratories do not have the necessary conditions), and the resulting 2-aryl or alkenyl-modified glycosides inevitably contain axial and equatorial isomers, which are usually difficult to separate. J. Am. Chem. Soc. 2022, 144, 3353; J. Am. Chem. Social The limited availability of this method (e.g., 2021, 143, 8590) greatly restricts its widespread application. Therefore, developing a novel, efficient, and mild synthetic method for C2-functionalized glycoenes or glycosides has significant application value. Summary of the Invention

[0004] To address the aforementioned shortcomings of existing technologies, this invention provides a glycoene sulfonium salt, its synthetic method, and its applications. By adding a base to suppress byproducts, the target product can be obtained in an excellent yield of 85-99%, without the need for column chromatography purification, demonstrating the promising potential of our synthetic method.

[0005] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows: A glycoene sulfonium salt is provided, wherein a dibenzohexane sulfonium group centered on a tetravalent thiocation is attached to the C-2 position of the glycoene unit of the glycoene salt, and the double bond of the glycoene unit is directly connected to the thiocation to form a stable glycoene sulfonium structure; its structural formula is shown in Formula I below. ; Wherein, RO is a protecting group, and RO is one or more combinations of acetoxy, methoxy, tert-butyldimethylsiloxy, triisopropylsiloxy and glycosyl; X is S, O, NR or two benzene rings directly connected without heteroatom bridging in between; n is 0 or 1.

[0006] Furthermore, the sugarene sulfonium salt is any one of the following compounds; ; Among them, TT is thiaanthracene-5-onyl; compounds 2a, 2d, 2m, 2n and 2o have only methoxy protecting groups; compounds 2b, 2c, 2e, 2f, 2h and 2k have only acetoxy protecting groups; compound 2g has only tert-butyldimethylsiloxy protecting groups; compounds 2i and 2l have a combination of methoxy and triisopropylsiloxy protecting groups; and compound 2j has a combination of acetoxy and triisopropylsiloxy protecting groups. The X group of compound 2m is NR, the X group of compound 2n is O, compound 2o consists of two benzene rings directly connected without any heteroatom bridging them, and the X group of the other compounds is S.

[0007] A method for synthesizing the above-mentioned syrenesinium salt is also provided, comprising the following steps: A1: Add a glycoene substrate with a protecting group, a dibenzohexacyclic sulfoxide compound and 2,6-di-tert-butyl-4-methylpyridine to dichloromethane, place the mixture in an ice bath at 0°C, then add trifluoromethanesulfonic anhydride, and after adding trifluoromethanesulfonic anhydride, place the reaction system at room temperature for 20 min. A2: After the reaction is completed, the reactants are diluted with dichloromethane, washed with NaBF4 solution, dried with anhydrous Na2SO4, filtered, and the solvent is evaporated to obtain the crude product. A3: The crude product was recrystallized using a dichloromethane:n-hexane ratio of 1:5~20 to obtain saccharene sulfonium salt.

[0008] Furthermore, the molar ratio of the glycoene substrate, dibenzohexacyclic sulfoxide compound, 2,6-di-tert-butyl-4-methylpyridine, and trifluoromethanesulfonic anhydride is 1:1.1:2:1.2.

[0009] Furthermore, when the glycoene sulfonium salt is 2a, the glycoene substrate structure is shown in Formula 1a below; ; When the glycoene sulfonium salt is 2b, the glycoene substrate structure is shown in the following formula S1; ; When the glycoene sulfonium salt is 2c, the glycoene substrate structure is shown in formula S3 below; ; When the glycoene sulfonium salt is 2d, the glycoene substrate structure is shown in Formula 1b below; ; When the glycoene sulfonium salt is 2e, the glycoene substrate structure is shown in Equation 1c below; ; When the glycoene sulfonium salt is 2f, the glycoene substrate structure is shown in Equation 1d below; ; When the amount of glycoene sulfonium salt is 2g, the structural formula of the glycoene substrate is shown in Formula 1e below; ; When the glycoene sulfonium salt is 2h, the glycoene substrate structure is shown in Formula 1f below; ; When the glycoene sulfonium salt is 2i, the glycoene substrate structure is shown in Formula 1g below; ; When the glycoene sulfonium salt is 2j, the glycoene substrate structure is shown in Equation 1h below; ; When the glycoene sulfonium salt is 2k, the glycoene substrate structure is shown in Equation 1i below; ; When the glycoene sulfonium salt is 2l, the glycoene substrate structure is shown in Formula 1j below; ; When the sucrane sulfonium salts are 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, 2j, 2k, and 2l, the dibenzohexacyclic sulfoxides are all thiaanthracene-5-oxides; When the glycoene sulfonium salt is 2m, the glycoene substrate structure is shown in Equation 1a below; ; Furthermore, the dibenzohexacyclic sulfoxide compound is 10-methylphenthiazine-10-oxide, and its structural formula is shown in Formula II below; ; When the glycoene sulfonium salt is 2n, the glycoene substrate structure is shown in Equation 1a below; ; Furthermore, the dibenzohexacyclic sulfoxide compound is phenoxathia-10-oxide, and its structural formula is shown in Formula III below; ; When the glycoene sulfonium salt is 2o, the glycoene substrate structure is shown in Formula 1a below; ; Furthermore, the dibenzohexacyclic sulfoxide compound is dibenzothiophene-5-oxide, and its structural formula is shown in Formula IV below; .

[0010] Furthermore, the synthetic method for glycoene substrate 1c is as follows: B1: Dissolve L-arabinose in pyridine, then add acetic anhydride. After the reaction is complete at room temperature, add EA to dilute the system, wash with 1M HCl and saturated brine in sequence, dry with anhydrous Na2SO4, filter, and evaporate the solvent to obtain the first intermediate product. B2: The first intermediate obtained was dissolved in DCM, and 33% HBr / AcOH was added under ice bath. The reaction was brought back to room temperature for 1 hour. After the reaction was completed, DCM was added to the system to dilute it. The system was washed successively with saturated sodium bicarbonate solution and saturated brine, then dried with anhydrous Na2SO4, filtered, and the solvent was evaporated to obtain the second intermediate. B3: The obtained second intermediate product and zinc powder were dissolved in acetone, and then saturated NaH2PO4 solution was added. The mixture was reacted at room temperature for 3 hours. After the reaction was completed, the mixture was filtered, and the filtrate was diluted with EA, washed with saturated brine, dried with anhydrous Na2SO4, filtered, and the solvent was evaporated. The mixture was then purified by column chromatography using PE:EA = 3:1 to obtain glycoene substrate 1c.

[0011] Furthermore, the synthetic method for glycoene substrate 1e is as follows: C1: Dissolve 2'-deoxythymidine in DMF, then add DMAP and imidazole, add TBSCl under ice bath, and after the reaction is complete at room temperature, add H2O and continue stirring. After filtering and washing the filter cake with water, recrystallize it with MTBE and n-hexane at -40℃ to obtain the third intermediate product. C2: The obtained third intermediate, ammonium sulfate and BHT were dissolved in n-heptane, and HMDS was added. The mixture was heated to 140℃ and refluxed for 34 h. After the reaction was completed, the mixture was restored to room temperature, and 2,4,6-trimethylpyridine and ethanol were added. After stirring for 2 h, the mixture was filtered. The filter cake was washed with cyclopentyl methyl ether, and the filtrate was concentrated to obtain glycoene substrate 1e.

[0012] Furthermore, the method for synthesizing 1g of the glycoene substrate is as follows: D1: Dissolve D-galactosene in DMF, add imidazole, add TIPSCl under ice bath, restore to room temperature and react overnight. After the reaction is complete, add EA to dilute, wash with saturated sodium chloride, concentrate, and purify by column chromatography with PE:EA=8:1 to obtain the fourth intermediate. D2: Dissolve the fourth intermediate in DMF, add NaH under ice bath, react for 20 min, add MeI, restore to room temperature and react overnight, add EA to dilute after the reaction, wash with saturated sodium chloride, concentrate, and purify by column chromatography with PE:EA = 20:1 to obtain 1 g of glycoene substrate.

[0013] The present invention also provides an application of the above-mentioned glycoene sulfonium salt in the preparation of 2-functionalized glycoside compounds, wherein the glycoene sulfonium salt participates in Suzuki coupling, Sonogashira coupling, Heck coupling or Hiyama coupling to synthesize 2-functionalized glycoside compounds.

[0014] The beneficial effects of this invention are as follows: This invention proposes a DHSO-Tf₂O-DTBMP system by adding a base to suppress byproducts. This system can efficiently synthesize monosaccharide and disaccharide sulfonium salts with different protecting groups in excellent yields of 85-99%. In the sulfonium salt, a dibenzohexacyclic sulfonium group centered on a tetravalent thiocation is attached to the C-2 position of the sulfonium unit, and the double bond of the sulfonium unit is directly linked to the thiocation, forming a stable sulfonyl sulfonium structure. The entire synthetic reaction is simple to operate, requiring only 20 minutes, and eliminates the need for column chromatography separation and purification, saving cumbersome steps and making it suitable for large-scale synthesis.

[0015] Meanwhile, the prepared sucrane sulfonium salts can serve as synthetic precursors to achieve direct functionalization at the 2-position of sucrane, thereby efficiently synthesizing 2-aryl glycosides, 2-alkynyl glycosides, and 2-enyl glycosides. Compared to 2-haloglycoenes, sucrane sulfonium salts offer advantages such as simple preparation, rapid reaction, high yield, no need for metals or toxic reagents, and no need for column chromatography separation and purification. Moreover, sucrane sulfonium salts exhibit good functional group compatibility, being compatible with acid-sensitive silicon-based protecting groups. Their reactivity is higher than that of 2-iodoglycoenes, resulting in higher yields in synthetic transformations such as Suzuki coupling. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the synthetic route for glycoene sulfonium salts. Detailed Implementation

[0017] The specific embodiments of the present invention are described below to enable those skilled in the art to understand the present invention. However, it should be understood that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, various changes are obvious as long as they are within the spirit and scope of the present invention as defined and determined by the appended claims. All inventions utilizing the concept of the present invention are protected.

[0018] Unless otherwise specified, all raw materials used in the examples are commercially available analytical grade.

[0019] Example 1 Synthesis of saccharene sulfonium salt Adopting such Figure 1 The synthetic route shown below synthesizes glycoene sulfonium salts. The specific steps are as follows: A1: A glycoene substrate with a protecting group, a dibenzohexane sulfoxide compound (DHSO), and 2,6-di-tert-butyl-4-methylpyridine were added to dichloromethane. The mixture was placed in an ice bath at 0°C, and then trifluoromethanesulfonic anhydride was added. After adding trifluoromethanesulfonic anhydride, the reaction mixture was placed at room temperature for 20 min. The molar ratio of the glycoene substrate, the dibenzohexane sulfoxide compound, 2,6-di-tert-butyl-4-methylpyridine, and trifluoromethanesulfonic anhydride was 1:1.1:2:1.2.

[0020] A2: After the reaction is completed, the reactants are diluted with dichloromethane, washed with NaBF4 solution, dried with anhydrous Na2SO4, filtered, and the solvent is evaporated to obtain the crude product. A3: The crude product was recrystallized using a dichloromethane:n-hexane system to obtain saccharene sulfonium salt.

[0021] Sugar sulfonium salts include the following compounds: ; To investigate the effects of different types of alkali additives and acid anhydride additives on the synthesis process, the synthesis of compound 2a was used as an example. Except for the type of additive, all other experimental conditions were kept consistent, and dibromomethane was used as an internal standard. 1 1H NMR analysis was used to determine the yield of compound 2a. The results are shown in Table 1. Table 1

[0022] As shown in Table 1, when using the method of the present invention, the yield of compound 2a is high at 42% when DTBMP is used as the alkali additive and Tf2O is used as the acid anhydride additive. The yields of other combinations are all no more than 20%.

[0023] Furthermore, to investigate the effect of solvent on the synthesis process, experiments were conducted using the synthesis of compound 2a as an example. DTBMP was selected as the base additive, Tf₂O as the acid anhydride additive, and different solvents were used for synthesis. Except for the type of solvent, all other experimental conditions were the same. Dibromomethane was used as an internal standard. 1 1H NMR analysis was used to determine the yield of compound 2a. The results are shown in Table 2. Table 2

[0024] As shown in Table 2, when using dichloromethane as a solvent, the yield of compound 2a is the highest using the method of the present invention.

[0025] Example 2 Synthesis of sucrane sulfonium salt 2a The synthesis of glycoene sulfonium salt 2a uses glycoene substrate 1a, and the synthesis method of glycoene substrate 1a is as follows: Compound S1 (1 g, 3.7 mmol) was dissolved in 20 mL of methanol, and sodium methoxide was added to adjust the pH of the reaction solution to 8. The reaction was carried out at room temperature for 1 h. After the reaction was completed, the pH of the reaction system was adjusted to 8, and the solvent was evaporated to obtain compound S2 as a viscous syrup (515 mg, 96%). Next, compound S2 (1 g, 6.85 mmol, 1 equivalent) was dissolved in DMF, and NaH (986 mg, 41.1 mmol, 6 equivalent) was added under ice bath conditions. After stirring for 20 min, MeI (2.56 mL, 41.1 mmol, 6 equivalent) was slowly added. After the addition was completed, the mixture was brought to room temperature and reacted overnight. After the reaction was completed, the mixture was quenched with ice water, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, evaporated to dryness, and purified by column chromatography (PE:EA = 8:1) to obtain the syrup, namely compound 1a (1.18 g, 92%).

[0026] NMR analysis of compound 1a yielded the following results: 1 H NMR (400 MHz, CDCl3) d 6.39 (dd, J =6.1, 1.5 Hz, 1H), 4.85-4.80 (m, 1H), 4.00-3.93 (m, 1H), 3.88 (ddt, J = 6.1,2.9, 1.5 Hz, 1H), 3.70-3.62 (m, 2H), 3.54 (d, J = 1.7 Hz, 3H), 3.46 (dd, J =8.2, 6.2 Hz, 1H), 3.41 (d,J = 1.7 Hz, 3H), 3.40 (d, J = 1.7 Hz, 3H). Following the method of Example 1, glycoene substrate 1a and thiaanthra-5-oxide (a dibenzohexane sulfoxide) were used for synthesis. The glycoene substrate 1a was set to 1 equiv. = 0.1 mmol. The resulting brownish-yellow foamy solid was glycoene sulfonium salt 2a (43.6 mg, 89%). Its NMR results were as follows: 1 H NMR (400 MHz, CDCl3) d 8.25 (d, J = 7.5Hz, 2H), 7.74 (d, J = 8.1 Hz, 4H), 7.65 (d, J = 7.4 Hz, 2H), 7.18 (s, 1H), 4.43-4.33 (m, 1H), 3.82 (d, J = 4.0 Hz, 1H), 3.67 (t, J = 4.4 Hz, 1H), 3.56(dd, J = 10.8, 6.3 Hz, 1H), 3.45 (dd, J = 10.8, 4.4 Hz, 1H), 3.30 (s, 3H), 3.29 (s, 3H), 3.23 (s, 3H). Example 3 Synthesis of 2b syrenesium salt The synthesis of sucrane sulfonium salt 2b was performed using sucrane substrate S1, following the method described in Example 1. The sucrane substrate S1 was used, and the dibenzohexacyclic sulfoxide compound was thiaanthracene-5-oxide. The sucrane substrate S1 was set to 1 equiv. = 0.1 mmol. The resulting product was a brownish-yellow foamy solid, namely sucrane sulfonium salt 2b (51.7 mg, 91%). Its NMR results were as follows: 1 H NMR (400 MHz, CDCl3) d 8.45 (d, J = 7.7 Hz, 2H), 7.79-7.66 (m, 6H), 7.64 (d, J = 3.9Hz, 1H), 5.12 (t, J = 2.8 Hz, 1H), 5.07-5.02 (m, 1H), 4.59 (td, J = 5.7, 2.9Hz, 1H), 4.32 (dd, J= 12.2, 7.7 Hz, 1H), 4.15 (dd, J = 12.2, 5.1 Hz, 1H), 2.04(s, 3H), 1.89 (s, 3H), 1.85 (s, 3H). Example 4 Synthesis of 2c sugarene sulfonium salt The synthesis of sucrane sulfonium salt 2c used sucrane substrate S3, following the method described in Example 1. The sucrane substrate S3 was used, and the dibenzohexane sulfoxide compound was thiaanthracene-5-oxide. The sucrane substrate S3 was set at 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely sucrane sulfonium salt 2c (55.8 mg, 97%). Its NMR results are as follows: 1 H NMR (400MHz, CDCl3) d 8.36 (d, J = 7.8 Hz, 1H), 8.25 (d, J = 7.9 Hz, 1H), 7.78-7.64 (m,6H), 7.02 (s, 1H), 5.47-5.37 (m, 2H), 4.60-4.52 (m, 1H), 4.23-4.16 (m, 2H), 2.06 (s, 3H), 2.02 (s, 3H), 1.86 (s, 3H). Example 5 Synthesis of 2d sugarene sulfonium salt The synthesis of glycoene sulfonium salt 2d uses glycoene substrate 1b, and the synthesis method of glycoene substrate 1b is as follows: Compound S3 (1 g, 3.7 mmol) was dissolved in 20 mL of methanol, and sodium methoxide was added to adjust the pH of the reaction solution to 8. The reaction was carried out at room temperature for 1 h. After the reaction was completed, the pH of the reaction system was adjusted to 8, and the solvent was evaporated to obtain compound S4 as a viscous liquid (526 mg, 98%). Next, compound S4 (1 g, 6.85 mmol, 1 equivalent) was dissolved in DMF, and NaH (986 mg, 41.1 mmol, 6 equivalent) was added under ice bath conditions. After stirring for 20 min, MeI (2.56 mL, 41.1 mmol, 6 equivalent) was slowly added. After the addition was completed, the reaction was allowed to proceed at room temperature overnight. After the reaction was completed, the mixture was quenched with ice water, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, evaporated to dryness, and purified by column chromatography (PE:EA = 8:1) to obtain compound 1b as an oily liquid (1.2 g, 92%).

[0027] NMR analysis of compound 1b yielded the following results: 1 H NMR (400 MHz, CDCl3) d 6.29 (dd, J =6.3, 1.3 Hz, 1H), 4.77 (ddd, J = 6.2, 3.0, 1.0 Hz, 1H), 4.15-4.07 (m, 1H), 3.96-3.88 (m, 1H), 3.65 (dd, J = 10.2, 7.6 Hz, 2H), 3.54 (dd, J = 10.2, 4.9 Hz,1H), 3.50 (s, 3H), 3.37 (s, 3H), 3.34 (s, 3H). Following the method of Example 1, glycoene substrate 1b and thiaanthra-5-oxide (a dibenzohexane sulfoxide) were used for synthesis. The glycoene substrate 1b was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely glycoene sulfonium salt 2d (42.5 mg, 87%). Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.21-8.11 (m, 2H),7.79-7.66 (m, 6H), 6.65 (s, 1H), 4.58 (t, J = 6.4 Hz, 1H), 4.38-4.33 (m, 1H), 4.07 (d, J = 3.4 Hz, 1H), 3.68 (d, J = 6.4 Hz, 2H), 3.55 (s, 3H), 3.37 (s, 3H), 3.21 (s, 3H). Example 6 Synthesis of 2e- ... The synthesis of glycoene sulfonium salt 2e uses glycoene substrate 1c. The synthesis method of glycoene substrate 1c is as follows: L-arabinose, compound S5 (1 g, 6.67 mmol), was dissolved in pyridine (20 mL), followed by the addition of acetic anhydride (3.8 mL, 40.2 mmol, 6 equiv.). The reaction was carried out at room temperature for 3 h, and TLC was used to monitor the complete reaction of the substrate. The solvent was then evaporated to obtain the first intermediate compound S6. Compound S6 was dissolved in DCM (20 mL), and 33% HBr / AcOH (11 mL, 67 mmol, 10 equiv.) was added under ice bath conditions. The reaction was then allowed to return to room temperature for 1 h, and TLC was used to monitor the complete reaction of the substrate. D2O3 was added to the system. CM was diluted, washed with saturated sodium bicarbonate solution and saturated brine respectively, dried over anhydrous Na2SO4, filtered, and the solvent was evaporated to obtain the second intermediate compound S7; compound S7 and zinc powder (2.2 g) were dissolved in acetone (10 mL), and saturated NaH2PO4 solution (4 mL) was added. The reaction was carried out at room temperature for 3 h. After the reaction was completed, the mixture was filtered, diluted with EA, washed with saturated brine, dried over anhydrous Na2SO4, filtered, the solvent was evaporated, and purified by column chromatography (PE∶EA=3∶1) to obtain compound 1c (1.1 g, 83%).

[0028] NMR analysis of compound 1c yielded the following results: 1 ¹H NMR (300 MHz, CDCl₃) d 6.48 (d, J = 5.7Hz, 1H), 5.42 (app t, J = 4.2 Hz, 1H), 5.17 (ddd, J = 3.9, 6.4, 8.4 Hz, 1H),4.82 (app t, J = 5.1 Hz, 1H), 3.93-4.00 (m, 2H), 2.07 (s, 3H), 2.06 (s, 3H). Using the method of Example 1, glycoene substrate 1c and thiaanthra-5-oxide as a dibenzohexane sulfoxide were synthesized. The glycoene substrate 1c was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely glycoene sulfonium salt 2e (46 mg, 92%). Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) d 8.30 (d, J = 7.9 Hz,2H), 7.75-7.65 (m, 7H), 5.58 (d, J = 3.4 Hz, 1H), 5.05 (dd, J= 9.5, 5.3 Hz, 1H), 4.21 (dd, J = 11.2, 4.3 Hz, 1H), 4.07 (t, J = 11.0 Hz, 1H), 1.94 (s, 3H), 1.74 (s, 3H). Example 7 Synthesis of 2f syrenesium salt The synthesis of glycoene sulfonium salt 2f uses glycoene substrate 1d. The synthesis method of glycoene substrate 1d is as follows: D-fucose, i.e., compound S8 (1 g, 6.10 mmol), was dissolved in pyridine (20 mL), followed by the addition of acetic anhydride (3.5 mL, 40.2 mmol, 6 equiv.). The reaction was carried out at room temperature for 3 h, and the substrate was monitored by TLC until complete reaction. The solvent was then evaporated to obtain compound S9. Compound S9 was dissolved in DCM (20 mL), and 33% HBr / AcOH (10 mL, 61 mmol, 10 equiv.) was added under ice bath conditions. The reaction was then brought back to room temperature and carried out for 1 h, with the substrate being monitored by TLC until complete reaction. The reaction was carried out by diluting the system with DCM, washing with saturated NaHCO3, and drying the solvent to obtain compound S10. Compound S10 and zinc powder (2.0 g) were dissolved in acetone (10 mL), and saturated NaH2PO4 solution (4 mL) was added. The reaction was carried out at room temperature for 3 h. After the reaction was completed, the mixture was filtered, diluted with EA, washed with saturated brine, dried over anhydrous Na2SO4, filtered, dried the solvent, and purified by column chromatography (PE:EA = 3:1) to obtain compound 1d (1.0 g, 77%). The NMR analysis of compound 1d yielded the following results: 1 H NMR (500 MHz, CDCl3) d 6.34 (d, J = 2.9Hz, 1H), 5.38-5.29 (m, 3H), 4.28 (q, J = 7.1, 6.5 Hz, 1H), 2.18 (s, 3H), 2.15(s, 3H), 2.02 (s, 3H), 2.01 (s, 3H), 1.16 (d, J = 6.5 Hz, 3H). Following the method of Example 1, glycoene substrate 1d and thiaanthra-5-oxide (a dibenzohexane sulfoxide) were used for synthesis. The glycoene substrate 1d was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely glycoene sulfonium salt 2f (51.3 mg, 99%). Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) d 8.28 (d,J = 7.9 Hz, 1H), 8.17 (d, J = 7.9 Hz, 1H), 7.75-7.60 (m, 6H), 7.11 (s, 1H), 5.44 (d, J =4.2 Hz, 1H), 5.28 (dd, J = 4.3, 1.6 Hz, 1H), 4.52 (q, J = 6.6 Hz, 1H), 2.07 (s,3H), 1.76 (s, 3H), 1.28 (d, J = 6.7 Hz, 3H). Example 8 Synthesis of 2g of sucrane sulfonium salt The synthesis of 2g of glycoene sulfonium salt uses glycoene substrate 1e. The synthesis method of glycoene substrate 1e is as follows: 2'-Deoxythymidine, compound S11 (1 g, 4.13 mmol), was dissolved in 5 mL of DMF. DMAP (5 mg, 0.04 mmol, 0.01 equiv.) and imidazole (702 mg, 10.3 mmol, 2.5 equiv.) were added. TBSCl (1.58 mL, 9.1 mmol, 2.2 equiv.) was added under ice bath conditions. The reaction was brought to room temperature, and TLC was used to monitor complete substrate reaction. H2O was added and stirring continued. The filter cake was washed with water and recrystallized from MTBE and n-hexane at -40 °C to obtain compound S12. Compound S12, ammonium sulfate (50 mg, 0.38 mmol, 0.2 equiv.), and BHT (7.5 mg, 0.034 mmol, 0.01 equiv.) were dissolved in 17 mL of n-heptane. HMDS (2.33 mL, 11.1 mmol, 3.3 equiv.) was added, and the mixture was heated to 140 °C and refluxed for 34 h. After the reaction was completed, the mixture was brought back to room temperature, and 2,4,6-trimethylpyridine and ethanol were added. The mixture was stirred for 2 h and then filtered. The filter cake was washed with cyclopentyl methyl ether, and the filtrate was concentrated to give compound 1e, which was a dark red syrup (862 mg, 74%).

[0029] NMR analysis of compound 1a yielded the following results: 1 H NMR (400 MHz, CDCl3) d 6.39 (dd, J =6.1, 1.5 Hz, 1H), 4.85-4.80 (m, 1H), 4.00-3.93 (m, 1H), 3.88 (ddt, J= 6.1,2.9, 1.5 Hz, 1H), 3.70-3.62 (m, 2H), 3.54 (d, J = 1.7 Hz, 3H), 3.46 (dd, J =8.2, 6.2 Hz, 1H), 3.41 (d, J = 1.7 Hz, 3H), 3.40 (d, J = 1.7 Hz, 3H). Following the method of Example 1, a glycoene substrate 1e was used, and the dibenzohexane sulfoxide compound was thiaanthra-5-oxide. The glycoene substrate 1e was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely 2 g (49.5 mg, 93%) of glycoene sulfonium salt. Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) d 8.07 (t, J = 7.8 Hz, 2H), 7.89-7.61 (m, 7H), 5.25 (s, 1H), 4.94 (d, J = 5.8 Hz, 1H), 4.73 (dd, J =11.0, 4.8 Hz, 2H), 3.61 (d, J = 7.7 Hz, 1H), 3.38 (dd, J = 7.9, 3.8 Hz, 1H), 1.06 (s, 9H), 0.28 (s, 3H), 0.20 (s, 3H). Example 9 Synthesis of 2h glycoene sulfonium salt The synthesis of 2h glycoene sulfonium salts uses glycoene substrate 1f. The synthesis method of glycoene substrate 1f is as follows: Peracetyl 6-deoxy-D-glucose S13 (2 g, 6.10 mmol) was dissolved in DCM (20 mL), and 33% HBr / AcOH (10 mL, 61 mmol, 10 equiv.) was added under ice bath. The reaction was allowed to proceed to room temperature for 1 h. The substrate reaction was monitored by TLC until complete. The system was diluted with DCM and washed with saturated sodium bicarbonate solution and saturated brine, respectively. The solvent was evaporated to dryness to obtain compound S14. Compound S14 and zinc powder (2.0 g) were dissolved in acetone (10 mL), and saturated NaH2PO4 solution (4 mL) was added. The reaction was allowed to proceed to room temperature for 3 h. After the reaction was completed, the mixture was filtered, diluted with EA, washed with saturated brine, dried over anhydrous Na2SO4, filtered, and the solvent was evaporated to dryness. The mixture was purified by column chromatography (PE:EA = 3:1) to obtain compound 1f.

[0030] NMR analysis of compound 1f yielded the following results: 1 H NMR (400 MHz, CDCl3) d 6.43 (dd, J =6.2, 1.5 Hz, 1H), 5.34 (dddd, J = 6.1, 3.0, 1.5, 0.6 Hz, 1H), 5.03 (dd, J = 8.2, 6.1 Hz, 1H), 4.78 (dd, J = 6.1, 3.0 Hz, 1H), 4.18-4.05 (m, 1H), 2.09 (s, 3H), 2.04 (s, 3H), 1.31 (d, J = 6.6 Hz, 3H). Following the method of Example 1, glycoene substrate 1f and thiaanthra-5-oxide (a dibenzohexane sulfoxide) were used for synthesis. The glycoene substrate 1f was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely glycoene sulfonium salt 2h (49.6 mg, 96%). Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.33 (dt, J = 13.9,5.7 Hz, 2H), 7.70 (ddd, J = 26.1, 11.3, 6.1 Hz, 7H), 5.01 (dt, J = 3.4, 1.8 Hz, 1H), 4.94 (dt, J = 3.1, 1.7 Hz, 1H), 4.50 (q, J = 7.2 Hz, 1H), 1.86 (d, J = 1.5Hz, 3H), 1.79 (d, J = 1.7 Hz, 3H), 1.37-1.30 (m, 3H). Example 10 Synthesis of 2i syringe sulfonium salt The synthesis of glycoene sulfonium salt 2a uses 1 g of glycoene substrate. The synthetic method for 1 g of glycoene substrate is as follows: Compound S4 was synthesized using the method described in Example 5. Compound S4 (1 g, 6.85 mmol) was dissolved in DMF (20 mL), and imidazole (1.16 g, 17.1 mmol, 2.5 equiv.) was added. TIPSCl (2.2 mL, 10.3 mmol, 1.5 equiv.) was added under ice bath conditions, and the reaction was allowed to proceed overnight at room temperature. After the reaction was complete, EA was added for dilution, followed by washing with saturated sodium chloride, concentration, and purification by column chromatography (PE:EA = 8:1) to obtain compound S15 (1.18 g, 57%). Compound S15 was dissolved in 20 mL... In DMF, NaH (280 mg, 11.7 mmol, 3 equiv.) was added under ice bath conditions. After reacting for 20 min, MeI (0.73 mL, 11.7 mmol, 3 equiv.) was added, and the mixture was allowed to return to room temperature and reacted overnight. After the reaction was complete, EA was added for dilution, and the mixture was washed with saturated sodium chloride, concentrated, and purified by column chromatography (PE:EA = 20:1) to give 1 g (1.16 g, 90%) of the compound.

[0031] Using the method of Example 1, 1 g of glycoene substrate and thiaanthra-5-oxide as the dibenzohexane sulfoxide were used for synthesis. The glycoene substrate was set to 1 equiv. = 0.1 mmol. A brownish-yellow foamy solid, namely glycoene sulfonium salt 2i (55.6 mg, 88%), was obtained. Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) d 8.23 (d, J = 7.6Hz, 1H), 8.15 (d, J = 6.6 Hz, 1H), 7.74 (td, J = 16.7, 16.0, 8.1 Hz, 6H), 6.64(s, 1H), 4.38-4.29 (m, 2H), 4.05 (d, J = 3.3 Hz, 1H), 3.89 (dd, J = 7.2, 4.8 Hz,2H), 3.54 (s, 3H), 3.26 (s, 3H), 1.02 (d, J = 6.3 Hz, 21H). Example 11 Synthesis of 2j glycoene sulfonium salt The synthesis of glycoene sulfonium salt 2a uses glycoene substrate 1h. The synthesis method of glycoene substrate 1h is as follows: Compound S15 was synthesized using the method described in Example 10. Compound S15 (1 g, 3.3 mmol) and DMAP (80 mg, 0.66 mmol, 0.2 equiv.) were added to a reaction flask, followed by pyridine (10 mL) and acetic anhydride (0.93 mL, 9.9 mmol, 3 equiv.). The reaction was carried out at room temperature for 3 h. The reaction was monitored by TLC until the substrate was completely reacted. The mixture was diluted with EA, washed with 1 M HCl and saturated brine, dried over anhydrous Na2SO4, filtered, concentrated, and purified by column chromatography (PE:EA = 20:1) to obtain compound S15 as a colorless syrup (1.18 g, 93%).

[0032] Following the method of Example 1, a glycoene substrate of 1 h and a dibenzohexane sulfoxide compound of thiaanthra-5-oxide were used for synthesis. The glycoene substrate of 1 h was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely glycoene sulfonium salt 2j (58.4 mg, 85%). Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) d 8.40 (d, J = 7.6 Hz, 1H), 8.24 (d, J = 7.9 Hz, 1H), 7.74 (dd, J = 17.4, 8.1 Hz, 6H), 6.87 (s, 1H), 5.55 (d, J = 4.2 Hz, 1H), 5.32 (d, J = 4.2 Hz, 1H), 4.27 (t, J = 7.1 Hz, 1H), 3.84 (dd, J = 10.1, 6.1 Hz, 1H), 3.71 (dd, J = 10.1, 7.9 Hz, 1H), 2.08 (s, 3H), 1.93 (s, 3H), 0.97 (d, J = 5.7 Hz, 21H). Example 12 Synthesis of 2k syrenesium salt The synthesis of glycoene sulfonium salt 2k uses glycoene substrate 1i, and the synthesis method of glycoene substrate 1i is as follows: D-lactose (2.04 g, 2.92 mmol) and zinc powder (1.0 g) were dissolved in acetone (5 mL), and saturated NaH2PO4 solution (2 mL) was added. The mixture was reacted at room temperature for 3 h. After the reaction was completed, the mixture was filtered, diluted with EA, washed with saturated brine, dried over anhydrous Na2SO4, filtered, the solvent was evaporated, and purified by column chromatography (PE:EA = 1:1) to give compound 1i (1.16 g, 71%).

[0033] Following the method of Example 1, glycoene substrate 1i and thiaanthra-5-oxide (a dibenzohexane sulfoxide) were used for synthesis. The glycoene substrate 1i was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely glycoene sulfonium salt 2k (81.9 mg, 95%). Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) d 8.26 (d, J = 8.0 Hz, 1H), 8.17 (d, J = 7.9 Hz, 1H), 7.79-7.72 (m, 2H), 7.67 (dd, J = 25.8, 4.6 Hz,3H), 7.56 (s, 1H), 7.51 (s, 1H), 5.29-5.18 (m, 2H), 4.95-4.79 (m, 2H), 4.61(dd, J = 11.1, 5.7 Hz, 2H), 4.31 (dd, J = 12.3, 8.8 Hz, 1H), 4.20 (s, 1H), 4.05(dd, J = 12.3, 4.3 Hz, 1H), 3.95-3.83 (m, 2H), 3.75 (dd, J = 9.2, 4.5 Hz,1H), 2.10 (s, 3H), 1.98(d, J = 5.0 Hz, 9H), 1.89 (s, 3H), 1.76 (s, 3H). Example 13 Synthesis of 2l sucrane sulfonium salt The synthesis of glycoene sulfonium salt 2l was carried out using glycoene substrate 1j, which was synthesized using the synthetic method disclosed in the prior art "[1] Hongze L , Wei-Lin L , Kim HML , et al. Asymmetric syntheses of 8-oxabicyclo[3,2,1]octane and 11-oxatricyclo[5.3.1.0]undecane from glycals.[J].Chemical science,2017,8(9):6656-6661.DOI:10.1039 / c7sc02625k." Following the method of Example 1, glycoene substrate 1j and thiaanthra-5-oxide (a dibenzohexane sulfoxide) were used for synthesis. The glycoene substrate 1j was set to 1 equiv. = 0.1 mmol, yielding a yellow powdery solid, namely glycoene sulfonium salt 2l (55.7 mg, 88%). Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.32 (s, 2H), 7.76 –7.70 (m, 4H), 7.67 (d, J = 8.4 Hz, 2H), 7.10 (s, 1H), 4.21 (d, J = 5.5 Hz, 1H),3.92 – 3.81 (m, 3H), 3.74 (t, J = 4.9 Hz, 1H), 3.47 (q, J = 7.0 Hz, 1H), 3.35(s, 3H), 3.26 (s, 3H), 0.99 (d, J = 6.0 Hz, 21H). Example 14 Synthesis of 2m glycoene sulfonium salt The synthesis of glycoene sulfonium salt 2m uses glycoene substrate 1a. Glycoene substrate 1a is synthesized using the method of Example 2. Then, using the method of Example 1, glycoene substrate 1a and 10-methylphenothiazine-10-oxide (a dibenzohexacyclic sulfoxide) are synthesized. Specifically, compound 1a (18.8 mg, 0.1 mmol), 10-methylphenothiazine-10-oxide (25.2 mg, 0.11 mmol, 1.1 equiv.), and DTBMP (41 mg, 0. 20 mmol (2.0 equiv.) was added to 1 mL of dry DCM, and the mixture was placed in an ice bath at 0 °C. Tf₂O (20 μL, 0.12 mmol, 1.2 equiv.) was added, and the reaction was carried out at room temperature for 20 min. TLC monitoring showed the reaction was complete. The reaction mixture was diluted with DCM, washed with NaBF₄ solution, and the solvent was evaporated. The crude product was recrystallized from the DCM / n-hexane system to obtain a brownish-yellow powdery solid, namely 2m (44.8 mg, 92%) of syringesulfonium salt. Its NMR results were as follows: 1 H NMR (400 MHz, CDCl3) δ 7.91 (dd, J = 7.9, 1.6 Hz, 1H), 7.81 (dd, J = 7.9, 1.6 Hz, 1H), 7.78 – 7.70 (m, 2H), 7.49 (d, J = 8.6 Hz, 1H), 7.42 (d, J = 8.6 Hz, 1H),7.39 (s, 1H), 7.30 (t, J = 7.6 Hz, 2H), 4.41 – 4.31 (m, 1H), 3.75 (s, 3H),3.61 (t, J = 3.8 Hz, 1H), 3.54 (dd, J = 4.0, 1.6 Hz, 1H), 3.50 (dd, J = 10.7, 6.6 Hz, 1H), 3.38 (dd, J = 10.7, 4.7 Hz, 1H), 3.26 (s, 3H), 3.18 (s, 3H), 3.13 (s, 3H). Example 15 Synthesis of 2n glycoene sulfonium salt The synthesis of glycoene sulfonium salt 2n used glycoene substrate 1a. glycoene substrate 1a was synthesized using the method described in Example 2. Then, using the method described in Example 1, glycoene substrate 1a was used, with phenoxathia 10-oxide as the dibenzohexacyclic sulfoxide compound. The glycoene substrate 1a was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow powdery solid, namely glycoene sulfonium salt 2n (42.7 mg, 90%). Its NMR results are as follows: 1H NMR (400 MHz, CDCl3)δ 8.06 (s, 1H), 7.97 (dd,J = 8.0, 1.6 Hz, 1H), 7.91 (dd, J = 8.0, 1.6 Hz, 1H), 7.82 – 7.76 (m, 1H),7.71 (td, J = 7.9, 1.6 Hz, 1H), 7.54 – 7.47 (m, 2H), 7.45 – 7.39 (m, 2H), 4.42 (q, J = 5.3 Hz, 1H), 3.61 (t, J = 4.2 Hz, 1H), 3.50 (dd, J = 10.9, 6.1Hz, 1H), 3.44 (dd, J = 7.9, 5.8 Hz, 1H), 3.39 (q, J = 2.6 Hz, 1H), 3.26 (s,3H), 3.17 (s, 3H), 3.01 (s, 3H). Example 16 Synthesis of saccharene sulfonium salt 2o The synthesis of glycoene sulfonium salt 2o used glycoene substrate 1a. glycoene substrate 1a was synthesized using the method of Example 2; then, using the method of Example 1, glycoene substrate 1a and dibenzothiophene 5-oxide (a dibenzohexacyclic sulfoxide), the glycoene substrate 1a was set to 1 equiv. = 0.1 mmol, yielding a brownish-yellow foamy solid, namely glycoene sulfonium salt 2o (39.4 mg, 86%). Its NMR results are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 7.8 Hz, 1H), 8.11 (dd, J = 7.9, 4.9 Hz, 2H), 8.06 (t, J = 4.0 Hz, 2H), 7.82 (t, J =7.7 Hz, 1H), 7.75 (t, J = 7.7 Hz, 1H), 7.64 (t, J = 7.7 Hz, 1H), 7.59 (t, J =7.8 Hz, 1H), 4.52 (d, J = 5.2 Hz, 1H), 3.61 (dd, J = 10.9, 6.1 Hz, 1H), 3.53– 3.46 (m, 2H), 3.31 (s, 3H), 3.17 (s, 3H), 3.02 (d, J = 4.6 Hz, 1H), 2.46 (s, 3H). Example 17 Synthesis of 2-functionalized glycoside compounds Glycoside compounds with 2-position functionalization can be achieved through Suzuki coupling, Sonogashira coupling, Heck coupling, and Hiyama coupling; The specific method for synthesizing glycosides with 2-position functionalization via the Suzuki coupling reaction is as follows: 0.1 mmol of syringene sulfonium salt, arylboronic acid (0.15 mmol, 1.5 equiv.), and Pd ( t Bu3P)2 (0.005 mmol, 5 mol%) and NaHCO3 (0.3 mmol, 3.0 equiv.) were added to a reaction tube, purged three times with nitrogen, and 1 mL of acetone was added. The mixture was stirred overnight at 60 °C. After the reaction was complete, the mixture was diluted with EA, washed with saturated brine, dried over anhydrous sodium sulfate, and the organic phase was evaporated to dryness. The mixture was then purified by column chromatography to obtain the target compound.

[0034] The method for synthesizing 2-functionalized glycosides via Sonogashira coupling reaction is as follows: A glycoene sulfonium salt (0.1 mmol), Pd(dppf)Cl2 (0.003 mmol, 3 mol%), and CuI (0.02 mmol, 20 mol%) were dissolved in 1,4-dioxane. After three nitrogen purgings, DIPEA (0.2 mmol, 2.0 equiv.) and a terminal alkyne compound (0.15 mmol, 1.5 equiv.) were added, and the mixture was heated to 40 °C and reacted for 24 h. The resulting compound was purified by column chromatography to obtain the target compound.

[0035] The specific method for synthesizing glycosides with 2-functionalized groups via Heck coupling reaction is as follows: 0.1 mmol of glycoene sulfonium salt, 0.01 mmol (10 mol%) of Pd2(dba)3, and 0.2 mmol (2.0 equiv.) of potassium carbonate were dissolved in 1 mL of DMF, purged three times with nitrogen, and then an olefin (0.15 mmol (1.5 equiv.) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the product was purified by column chromatography to obtain the target compound.

[0036] The specific method for synthesizing glycosides with 2-position functionalization via the Hiyama coupling reaction is as follows: 0.1 mmol of glycoene sulfonium salt and Pd (… t Bu3P)2 (0.005 mmol, 5 mol%) was added to a reaction tube, purged three times with nitrogen, and then 1 mL of dry ethanol, aryltrimethoxysilane (0.2 mmol, 2 equiv.), and Et3N•3HF (0.3 mmol, 3.0 equiv.) were added. The mixture was stirred at 80 °C for 12 h. After the reaction was completed, the mixture was purified by column chromatography to obtain the target compound.

[0037] Example 18 Synthesis of 2-p-methoxyphenyl 3,4,6-trimethoxyglucoseene The synthesis of 2-p-methoxyphenyl 3,4,6-trimethoxyglucoseene was achieved by Suzuki coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the arylboronic acid was 4-methoxyphenylboronic acid. The compound 3a was purified by column chromatography (PE:EA=3:1) as a yellow liquid (24.3 mg, 83%). 1 H NMR (400 MHz, CDCl3) d 7.26–7.23 (m, 2H), 6.86 (dt, J = 8.8, 1.8 Hz, 2H), 6.71 (s, 1H), 4.36-4.29 (m, 1H), 4.19 (d, J = 3.8 Hz, 1H), 3.81-3.79 (m, 3H), 3.77-3.72 (m, 2H), 3.60 (ddd, J = 10.6,3.9, 1.7 Hz, 1H), 3.55 (d, J = 1.6 Hz, 3H), 3.42 (d, J = 1.5 Hz, 3H), 3.35 (d, J = 1.6 Hz, 3H). Compound 3a, namely 2-p-methoxyphenyl 3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0038] Example 19 Synthesis of 2-m-fluorophenyl 3,4,6-trimethoxyglucoseene The synthesis of 2-m-fluorophenyl 3,4,6-trimethoxyglucoseene was achieved by Suzuki coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the arylboronic acid was 3-fluorophenylboronic acid. The compound 3b was purified by column chromatography (PE:EA=4:1) as a colorless liquid (23.1 mg, 82%). 1H NMR (400 MHz, CDCl3) δ 7.26-7.19 (m, 1H),7.12-7.07 (m, 1H), 7.02 (dq, J = 10.8, 1.5 Hz, 1H), 6.89 (td, J = 8.2, 2.4Hz, 1H), 6.85 (d, J = 1.5 Hz, 1H), 4.39 (q, J = 5.7 Hz, 1H), 4.20-4.11 (m,1H), 3.80-3.71 (m, 2H), 3.59 (ddd, J = 10.5, 4.3, 1.5 Hz, 1H), 3.53 (d, J =1.6 Hz, 3H), 3.41 (d, J = 1.5 Hz, 3H), 3.39 (d, J = 1.5 Hz, 3H). Compound 3b, namely 2-m-fluorophenyl 3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0039] Example 20 Synthesis of 2-(2-naphthyl)-3,4,6-trimethoxyglucoseene The synthesis of 2-(2-naphthyl)3,4,6-trimethoxyglucoseene was achieved by Suzuki coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, the arylboronic acid was 2-naphthoboronic acid, and the compound 3c was purified by column chromatography (PE:EA=3:1) as a colorless liquid (24.2 mg, 77%). 1 ¹H NMR (400 MHz, CDCl₃) δ 7.83 – 7.72 (m, 4H), 7.52 – 7.39 (m, 3H), 6.95 (s, 1H), 4.40 (dt, J = 11.9, 4.2 Hz, 2H), 3.87 – 3.78 (m, 2H), 3.64 (dd, J = 10.5, 3.9 Hz, 1H), 3.58 (s, 3H), 3.44 (s, 3H), 3.40 (s, 3H). Compound 3c, namely 2(2-naphthyl)-3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0040] Example 21 Synthesis of 2-p-methylphenyl 3,4,6-trimethoxyglucoseene The synthesis of 2-p-methylphenyl 3,4,6-trimethoxyglucoseene was achieved by Suzuki coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the arylboronic acid was pyridine-4-boronic acid. The compound 3d was purified by column chromatography (PE:EA=3:1) as a yellow liquid (25.1 mg, 90%). 1 ¹H NMR (400 MHz, CDCl₃) δ 7.22 (d, J = 7.8 Hz, 2H), 7.12 (d, J = 7.9 Hz, 2H), 6.77 (s, 1H), 4.38 – 4.31 (m, 1H), 4.25 – 4.19 (m, 1H), 3.80 – 3.72 (m, 2H), 3.60 (dd, J = 10.6, 3.8 Hz, 1H), 3.55 (d, J = 1.1 Hz, 3H), 3.42 (d, J = 1.1 Hz, 3H), 3.36 (s, 3H), 2.33 (s, 3H). Compound 3d is 2-p-methylphenyl 3,4,6-trimethoxyglucoseene, with the following structural formula: .

[0041] Example 22 Synthesis of 2-o-Boc pyrrole-3,4,6-trimethoxyglucoseene The synthesis of 2-o-Boc pyrrole-3,4,6-trimethoxyglucose was achieved by Suzuki coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the arylboronic acid was 5-bromothiophene-2-boronic acid. The compound 3e was purified by column chromatography (PE:EA=3:1) as a yellow liquid (25.4 mg, 72%). 1 ¹H NMR (400 MHz, CDCl₃) δ 7.20 (dd, J = 3.3, 1.9 Hz, 1H), 6.56 (s, 1H), 6.09 – 5.99 (m, 3H), 5.30 (dd, J = 7.5, 5.9 Hz, 1H), 4.47 – 4.39 (m, 2H), 4.30 – 4.21 (m, 1H), 2.11 (s, 6H), 1.82 (s, 3H), 1.59 (s, 9H). Compound 3e is 2-o-Boc pyrroleyl-3,4,6-trimethoxyglucoseene, with the following structural formula: .

[0042] Example 23 Synthesis of 2-o-phenylpropionylfuranyl-3,4,6-trimethoxyglucoseene The synthesis of 2-o-phenylpropionylfuranyl-3,4,6-trimethoxyglucose ene was achieved by Suzuki coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the arylboronic acid was benzofuran-2-boronic acid. The compound 3f was purified by column chromatography (PE:EA=3:1) as a yellow liquid (26.5 mg, 87%). 1 ¹H NMR (400 MHz, CDCl₃) δ 7.50 – 7.36 (m, 3H), 7.24 – 7.12 (m, 2H), 6.38 (s, 1H), 5.84 (d, J = 3.3 Hz, 1H), 5.22 (t, J = 3.4 Hz, 1H), 4.59 – 4.48 (m, 2H), 4.27 (q, J = 7.6 Hz, 1H), 2.17 – 2.06 (m, 9H). Compound 3f, namely 2-o-phenylpropyryluryl 3,4,6-trimethoxyglucose, has the following structural formula: .

[0043] Example 24 Synthesis of 2-n-hexyneyl-3,4,6-trimethoxyglucoseene The synthesis of 2-n-hexynyl 3,4,6-trimethoxyglucose ene was achieved by Sonogashira coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the terminal alkyne compound was benzofuran-2-boronic acid. The compound was purified by column chromatography (PE:EA=8:1) to give 3g of the compound as a yellow liquid (21.6mg, 81%). 1 H NMR (400 MHz, CDCl3)δ 6.69 (s,1H), 4.12 (td, J = 6.3, 3.2 Hz, 1H), 3.79 (d, J = 4.9 Hz, 1H), 3.66 (dd, J =10.7, 6.2 Hz, 1H), 3.59-3.55 (m, 1H), 3.54 (s, 3H), 3.51 (s, 3H), 3.49-3.46(m, 1H), 3.38 (s, 3H), 2.30 (t, J = 7.0 Hz, 2H), 1.54-1.46 (m, 2H), 1.41 (q,J = 7.3 Hz, 2H), 0.90 (t, J = 7.2 Hz, 3H). Compound 3g, namely 2-n-hexynyl 3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0044] Example 25 Synthesis of 2-cyclopropylynyl 3,4,6-trimethoxyglucoseene The synthesis of 2-cyclopropylalkynyl 3,4,6-trimethoxyglucoseene was achieved by Sonogashira coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the terminal alkyne compound was cyclopropylacetylene. The compound 3h was purified by column chromatography (PE:EA=6:1) as a colorless liquid (20.9 mg, 83%). 1 H NMR (400 MHz, CDCl3)δ 6.69 (s, 1H),4.11 (td, J = 6.2, 3.2 Hz, 1H), 3.79 – 3.75 (m, 1H), 3.67 – 3.61 (m, 1H),3.57 (d, J = 3.3 Hz, 1H), 3.53 (d, J = 1.0 Hz, 3H), 3.51 – 3.49 (m, 3H), 3.47 (dd, J = 6.4, 5.1 Hz, 1H), 3.38 (d, J = 1.0 Hz, 3H), 1.37 – 1.30 (m, 1H), 0.76 (dt, J = 8.0, 3.1 Hz, 2H), 0.71 – 0.66 (m, 2H). Compound 3h, namely 2-cyclopropylynyl 3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0045] Example 26 Synthesis of 2-p-ethylphenylynyl 3,4,6-trimethoxyglucoseene The synthesis of 2-p-ethylbenzyne-3,4,6-trimethoxyglucoseene was achieved by Sonogashira coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the terminal alkyne compound was p-bromophenylacetylene. The compound 3i was purified by column chromatography (PE:EA=5:1) as a yellow liquid (24.7 mg, 78%). 1H NMR (400 MHz, CDCl3) δ 7.32 –7.27 (m, 2H), 7.12 (d, J = 7.9 Hz, 2H), 6.97 – 6.89 (m, 1H), 5.62 (d, J = 5.5Hz, 1H), 5.25 (dd, J = 7.1, 5.6 Hz, 1H), 4.43 (dd, J = 12.1, 6.0 Hz, 1H), 4.38 – 4.33 (m, 1H), 4.22 (dd, J = 12.1, 3.1 Hz, 1H), 2.63 (q, J = 7.6 Hz, 2H), 2.13 – 2.09 (m, 9H), 1.21 (t, J = 7.6 Hz, 3H). Compound 3i, namely 2-p-ethylphenylynyl 3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0046] Example 27 Synthesis of (E)-2-phenylvinyl 3,4,6-trimethoxyglucoseene The synthesis of (E)-2-phenylvinyl 3,4,6-trimethoxyglucoseene was achieved by Heck coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, the olefin was styrene, and the compound 3j was purified by column chromatography (PE:EA=8:1) as a yellow liquid (24.8 mg, 85%). 1 H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 7.7 Hz, 2H), 7.29 (t, J = 7.7 Hz, 2H), 7.17 (t, J = 7.4 Hz, 1H), 6.73 (s, 1H), 6.63 (d, J =16.2 Hz, 1H), 6.47 (d, J = 16.2 Hz, 1H), 4.42-4.34 (m, 1H), 4.16-4.11 (m, 1H), 3.74 (dt, J = 7.5, 5.0 Hz, 2H), 3.58 (dd, J = 10.4, 4.3 Hz, 1H), 3.54 (s, 3H), 3.49 (s, 3H), 3.40 (s, 3H). Compound 3j, namely (E)-2-phenylvinyl 3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0047] Example 28 Synthesis of (E)-2-ethyl acrylate-based 3,4,6-trimethoxyglucoseene The synthesis of (E)-2-ethyl acrylate-3,4,6-trimethoxyglucoseene was achieved by Heck coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, the olefin was ethyl acrylate, and the compound 3k was purified by column chromatography (PE:EA=3:1) as a yellow liquid (25.4 mg, 90%). 1 H NMR (400 MHz, CDCl3) δ 7.22 (s, 1H), 6.87(s, 1H), 5.78 (d, J = 15.7 Hz, 1H), 4.45 (p, J = 4.0 Hz, 1H), 4.19 (q, J =7.1 Hz, 2H), 3.98 – 3.90 (m, 1H), 3.73 – 3.66 (m, 2H), 3.55 – 3.50 (m, 1H), 3.50 – 3.46 (m, 3H), 3.44 (d, J = 1.3 Hz, 3H), 3.40 – 3.35 (m, 3H), 1.33 –1.24 (m, 3H). Compound 3k, namely (E)-2-ethyl acrylate 3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0048] Example 29 Synthesis of (E)-2-ethylene sulfone-3,4,6-trimethoxyglucoseene The synthesis of (E)-2-ethylenesulfonyl 3,4,6-trimethoxyglucoseene was achieved by Heck coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, and the olefin was phenylacetylene sulfone. The compound 3l was purified by column chromatography (PE:EA=2:1) ​​as a colorless liquid (34.7 mg, 98%). 1 H NMR (400 MHz, CDCl3) δ 7.93 – 7.83 (m, 2H), 7.60 – 7.48 (m, 3H), 7.21 (d, J = 15.1 Hz, 1H), 6.95 (s, 1H), 6.23 (d, J = 15.0 Hz, 1H), 4.39 (dd, J = 6.5, 3.8 Hz, 1H), 3.88 (d, J = 3.7 Hz, 1H), 3.67 (dt,J =15.4, 5.5 Hz, 2H), 3.52 (dd, J = 10.6, 4.4 Hz, 1H), 3.48 – 3.44 (m, 3H), 3.38– 3.35 (m, 3H), 3.34 – 3.31 (m, 3H). Compound 3l, namely (E)-2-ethylenesulfonyl 3,4,6-trimethoxyglucoseene, has the following structural formula: .

[0049] Example 30 Synthesis of (E)-2-methyl acrylate-based 3,4,6-trimethoxyglucoseene The synthesis of (E)-2-methyl acrylate-3,4,6-trimethoxyglucoseene was achieved by Heck coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2a, the olefin was methoxyacetylene, and the compound 3m was purified by column chromatography (PE:EA=3:1) as a yellow liquid (24.0 mg, 88%). 1 H NMR (400 MHz, CDCl3)δ 7.27 (d, J = 5.4 Hz,1H), 6.88 (s, 1H), 5.79 (d, J = 15.7 Hz, 1H), 4.45 (p, J = 4.0 Hz, 1H), 3.94(d, J = 2.7 Hz, 1H), 3.76 – 3.72 (m, 3H), 3.72 – 3.66 (m, 2H), 3.56 – 3.51 (m, 1H), 3.51 – 3.46 (m, 3H), 3.46 – 3.42 (m, 3H), 3.40 – 3.35 (m, 3H). Compound 3m is (E)-2-methyl acrylate-based 3,4,6-trimethoxyglucoseene, with the following structural formula: .

[0050] Example 31 Synthesis of 2-Phenylacetyl 3,4,6-Triacetylglucene The synthesis of 2-phenyl 3,4,6-triacetylglucose ene was achieved by Hiyama coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2b, and the aryltrimethoxysilane was phenyltrimethoxysilane. The compound 3n was purified by column chromatography (PE:EA = 5:1) as a colorless liquid (32.0 mg, 92%). 1¹H NMR (400 MHz, CDCl₃) δ 7.31 (t, J = 7.5 Hz, 2H), 7.22 (d, J = 7.6 Hz, 3H), 6.87 (s, 1H), 5.99 (d, J = 4.5 Hz, 1H), 5.28 (t, J = 5.3 Hz, 1H), 4.50 (dd, J = 11.8, 6.5 Hz, 1H), 4.43 (q, J = 5.9 Hz, 1H), 4.23 (dd, J = 12.0, 3.2 Hz, 1H), 2.12 (s, 3H), 2.10 (s, 3H), 1.93 (s, 3H). Compound 3n, namely 2-phenyl-3,4,6-triacetylglucoseene, has the following structural formula: .

[0051] Example 32 Synthesis of 2-(2-naphthyl)-3,4,6-triacetylglucoseene The synthesis of 2-(2-naphthyl)-3,4,6-triacetylglucose ene was achieved by Hiyama coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2b, and the aryltrimethoxysilane was 2-naphthyltrimethoxysilane. The compound 3o was purified by column chromatography (PE:EA=5:1) as a colorless liquid (36.3 mg, 91%). 1 H NMR (400 MHz, CDCl3) δ8.09 (d, J = 8.2 Hz, 1H), 7.87 – 7.78 (m, 2H), 7.49 (tt, J = 7.3, 5.7 Hz,2H), 7.42 (t, J = 7.6 Hz, 1H), 7.36 – 7.31 (m, 1H), 6.60 (s, 1H), 5.84 (d, J= 5.0 Hz, 1H), 5.42 (dd, J = 6.4, 5.0 Hz, 1H), 4.63 (dd, J = 11.9, 6.4 Hz,1H), 4.56 (dt, J = 9.6, 4.7 Hz, 1H), 4.32 (dd, J = 11.9 (1H, 3.2 Hz, 1H), 2.16 (s, 6H), 1.70 (s, 3H). Compound 3o, namely 2-(2-naphthyl)-3,4,6-triacetylglucoseene, has the following structural formula: .

[0052] Example 33 Synthesis of 2-p-methylphenyl 3,4,6-triacetylglucoseene The synthesis of 2-p-methylphenyl 3,4,6-triacetylglucose ene was achieved by Hiyama coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2b, and the aryltrimethoxysilane was p-tolyltrimethoxysilane. The compound 3p was purified by column chromatography (PE:EA=6:1) as a colorless liquid (26.8 mg, 74%). 1 ¹H NMR (400 MHz, CDCl₃) δ 7.11 (s, 4H), 6.83 (s, 1H), 5.96 (d, J = 4.5 Hz, 1H), 5.31 – 5.26 (m, 1H), 4.49 (dd, J = 11.9, 6.6 Hz, 1H), 4.42 (t, J = 4.9 Hz, 1H), 4.23 (dd, J = 11.8, 3.4 Hz, 1H), 2.32 (s, 3H), 2.11 (s, 3H), 2.10 (s, 3H), 1.93 (s, 3H). Compound 3p is 2-p-methylphenyl 3,4,6-triacetylglucoseene, with the following structural formula: .

[0053] Example 34 Synthesis of 2-(2-naphthyl)-3,4,6-trimethoxyglucoseene The synthesis of 2-(2-naphthyl)-3,4,6-trimethoxyglucoseene was achieved by Hiyama coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2m, and the aryltrimethoxysilane was 1-naphthyltrimethoxysilane. The compound 3q was purified by column chromatography (PE:EA=3:1) as a yellow liquid (25.2 mg, 82%). 1 H NMR (400 MHz, CDCl3) δ 8.18– 8.11 (m, 1H), 7.85 (dd, J = 7.3, 2.3 Hz, 1H), 7.80 – 7.77 (m, 1H), 7.50 –7.46 (m, 2H), 7.44 – 7.38 (m, 2H), 6.47 (s, 1H), 4.40 (s, 1H), 4.17 (d, J =4.7 Hz, 1H), 3.89 (dd, J = 10.5, 6.4 Hz, 1H), 3.77 – 3.72 (m, 2H), 3.61 (s,3H), 3.49 (d, J = 2.7 Hz, 4H), 3.03 (s, 3H). Compound 3q, namely 2-(2-naphthyl)-3,4,6-trimethoxyglucose, has the following structural formula: .

[0054] Example 34 Synthesis of 2-(2-naphthyl)-3,4,6-trimethoxygalactosene The synthesis of 2-(2-naphthyl)-3,4,6-trimethoxygalactosene was achieved by Hiyama coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 2d, and the aryltrimethoxysilane was 1-naphthyltrimethoxysilane. The compound 3r was purified by column chromatography (PE:EA=5:1) as a colorless liquid (25.1 mg, 80%). 1 H NMR (400 MHz, CDCl3) δ 8.11– 8.04 (m, 1H), 7.88 – 7.83 (m, 1H), 7.78 (d, J = 7.9 Hz, 1H), 7.51 – 7.46(m, 2H), 7.45 – 7.36 (m, 2H), 6.41 (s, 1H), 4.49 (dt, J = 7.8, 3.6 Hz, 1H), 4.35 (d, J = 3.8 Hz, 1H), 4.05 – 3.95 (m, 2H), 3.75 (dd, J = 10.6, 3.8 Hz, 1H), 3.64 (s, 3H), 3.49 (s, 3H), 3.09 (s, 3H). Compound 3r, namely 2-(2-naphthyl)-3,4,6-trimethoxygalactosene, has the following structural formula: .

[0055] Example 35 Synthesis of 2-(2-naphthyl)-3,4-dimethoxy-6-triisopropylsilylglucoseene The synthesis of 2-(2-naphthyl)-3,4-dimethoxy-6-triisopropylsilylglucose ene was achieved by Hiyama coupling, using the method described in Example 17. The glycoene sulfonium salt was compound 21, and the aryltrimethoxysilane was 1-naphthyltrimethoxysilane. The compound 3s was purified by column chromatography (PE:EA=8:1) as a colorless liquid (34.3 mg, 75%). 1H NMR (400 MHz, CDCl3) δ 8.16 (d, J = 8.6 Hz, 1H), 7.90 – 7.81 (m, 1H), 7.78 (d, J = 8.0 Hz,1H), 7.52 – 7.37 (m, 4H), 6.45 (s, 1H), 4.28 (q, J = 5.3 Hz, 1H), 4.17 (d, J= 4.4 Hz, 1H), 4.10 (h, J = 5.3 Hz, 2H), 3.88 (t, J = 5.0 Hz, 1H), 3.63 (s,3H), 3.04 (s, 3H), 2.13 – 2.04 (m, 1H), 1.20 – 1.10 (m, 21H). Compound 3S, namely 2-(2-naphthyl)-3,4-dimethoxy-6-triisopropylsilylglucoseene, has the following structural formula: .

Claims

1. A saccharene sulfonium salt, characterized in that, The glycoene unit of the glycoene salt is connected to a dibenzohexane sulfonium group centered on a tetravalent thiocation at the C-2 position, and the double bond of the glycoene unit is directly connected to the thiocation to form a stable glycoene sulfonium structure; its structural formula is shown in Formula I below. Wherein, RO is a protecting group, and RO is one or more combinations of acetoxy, methoxy, tert-butyldimethylsiloxy, triisopropylsiloxy and glycosyl; X is S, O, NR or two benzene rings directly connected without heteroatom bridging in between; n is 0 or 1.

2. The glycoene sulfonium salt according to claim 1, characterized in that, The glycoene sulfonium salt is any one of the following compounds; ； Among them, TT is thiaanthracene-5-onyl; compounds 2a, 2d, 2m, 2n and 2o have only methoxy protecting groups; compounds 2b, 2c, 2e, 2f, 2h and 2k have only acetoxy protecting groups; compound 2g has only tert-butyldimethylsiloxy protecting groups; compounds 2i and 2l have a combination of methoxy and triisopropylsiloxy protecting groups; and compound 2j has a combination of acetoxy and triisopropylsiloxy protecting groups. The X group of compound 2m is NR, the X group of compound 2n is O, compound 2o consists of two benzene rings directly connected without any heteroatom bridging them, and the X group of the other compounds is S.

3. A method for synthesizing the glycoene sulfonium salt according to claim 2, characterized in that, The following steps are used: A1: Add a glycoene substrate with a protecting group, a dibenzohexacyclic sulfoxide compound and 2,6-di-tert-butyl-4-methylpyridine to dichloromethane, place the mixture in an ice bath at 0°C, then add trifluoromethanesulfonic anhydride, and after adding trifluoromethanesulfonic anhydride, place the reaction system at room temperature for 20 min. A2: After the reaction is completed, the reactants are diluted with dichloromethane, washed with NaBF4 solution, dried with anhydrous Na2SO4, filtered, and the solvent is evaporated to obtain the crude product. A3: The crude product was recrystallized using a dichloromethane:n-hexane ratio of 1:5~20 to obtain saccharene sulfonium salt.

4. The synthesis method according to claim 3, characterized in that, The molar ratio of glycoene substrate, dibenzohexacyclic sulfoxide compound, 2,6-di-tert-butyl-4-methylpyridine and trifluoromethanesulfonic anhydride was 1:1.1:2:1.

2.

5. The synthesis method according to claim 3, characterized in that, When the glycoene sulfonium salt is 2a, the glycoene substrate structure is shown in Formula 1a below; ； When the glycoene sulfonium salt is 2b, the glycoene substrate structure is shown in the following formula S1; ； When the glycoene sulfonium salt is 2c, the glycoene substrate structure is shown in formula S3 below; ； When the glycoene sulfonium salt is 2d, the glycoene substrate structure is shown in Formula 1b below; ； When the glycoene sulfonium salt is 2e, the glycoene substrate structure is shown in Equation 1c below; ； When the glycoene sulfonium salt is 2f, the glycoene substrate structure is shown in Equation 1d below; ； When the amount of glycoene sulfonium salt is 2g, the structural formula of the glycoene substrate is shown in Formula 1e below; ； When the glycoene sulfonium salt is 2h, the glycoene substrate structure is shown in Formula 1f below; ； When the glycoene sulfonium salt is 2i, the glycoene substrate structure is shown in Formula 1g below; ； When the glycoene sulfonium salt is 2j, the glycoene substrate structure is shown in Equation 1h below; ； When the glycoene sulfonium salt is 2k, the glycoene substrate structure is shown in Equation 1i below; ； When the glycoene sulfonium salt is 2l, the glycoene substrate structure is shown in Formula 1j below; ； When the sucrane sulfonium salts are 2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i, 2j, 2k, and 2l, the dibenzohexacyclic sulfoxides are all thiaanthracene-5-oxides; When the glycoene sulfonium salt is 2m, the glycoene substrate structure is shown in Formula 1a below; ； Furthermore, the dibenzohexacyclic sulfoxide compound is 10-methylphenthiazine-10-oxide, and its structural formula is shown in Formula II below; ； When the glycoene sulfonium salt is 2n, the glycoene substrate structure is shown in Equation 1a below; ； Furthermore, the dibenzohexacyclic sulfoxide compound is phenoxathia-10-oxide, and its structural formula is shown in Formula III below; ； When the glycoene sulfonium salt is 2o, the glycoene substrate structure is shown in Formula 1a below; ； Furthermore, the dibenzohexacyclic sulfoxide compound is dibenzothiophene-5-oxide, and its structural formula is shown in Formula IV below; 。 6. The synthesis method according to claim 5, characterized in that, The method for synthesizing the glycoene substrate 1c is as follows: B1: Dissolve L-arabinose in pyridine, then add acetic anhydride. After the reaction is complete at room temperature, add EA to dilute the system, wash with 1M HCl and saturated brine in sequence, dry with anhydrous Na2SO4, filter, and evaporate the solvent to obtain the first intermediate product. B2: The first intermediate obtained was dissolved in DCM, and 33% HBr / AcOH was added under ice bath. The reaction was brought back to room temperature for 1 hour. After the reaction was completed, DCM was added to the system to dilute it. The system was washed successively with saturated sodium bicarbonate solution and saturated brine, then dried with anhydrous Na2SO4, filtered, and the solvent was evaporated to obtain the second intermediate. B3: The obtained second intermediate product and zinc powder were dissolved in acetone, and then saturated NaH2PO4 solution was added. The mixture was reacted at room temperature for 3 hours. After the reaction was completed, the mixture was filtered, and the filtrate was diluted with EA, washed with saturated brine, dried with anhydrous Na2SO4, filtered, and the solvent was evaporated. The mixture was then purified by column chromatography using PE:EA = 3:1 to obtain glycoene substrate 1c.

7. The synthesis method according to claim 5, characterized in that, The method for synthesizing the glycoene substrate 1e is as follows: C1: Dissolve 2'-deoxythymidine in DMF, then add DMAP and imidazole, add TBSCl under ice bath, and after the reaction is complete at room temperature, add H2O and continue stirring. After filtering and washing the filter cake with water, recrystallize it with MTBE and n-hexane at -40℃ to obtain the third intermediate product. C2: The obtained third intermediate, ammonium sulfate and BHT were dissolved in n-heptane, and HMDS was added. The mixture was heated to 140℃ and refluxed for 34 h. After the reaction was completed, the mixture was restored to room temperature, and 2,4,6-trimethylpyridine and ethanol were added. After stirring for 2 h, the mixture was filtered. The filter cake was washed with cyclopentyl methyl ether, and the filtrate was concentrated to obtain glycoene substrate 1e.

8. The synthesis method according to claim 5, characterized in that, The method for synthesizing 1g of the glycoene substrate is as follows: D1: Dissolve D-galactosene in DMF, add imidazole, add TIPSCl under ice bath, restore to room temperature and react overnight. After the reaction is complete, add EA to dilute, wash with saturated sodium chloride, concentrate, and purify by column chromatography with PE:EA=8:1 to obtain the fourth intermediate. D2: Dissolve the fourth intermediate in DMF, add NaH under ice bath, react for 20 min, add MeI, restore to room temperature and react overnight, add EA to dilute after the reaction, wash with saturated sodium chloride, concentrate, and purify by column chromatography with PE:EA = 20:1 to obtain 1 g of glycoene substrate.

9. The use of the glycoene sulfonium salt according to claim 1 in the preparation of 2-functionalized glycoside compounds, characterized in that, The glycoene sulfonium salt is used to synthesize glycoside compounds with 2-position functionalization by participating in Suzuki coupling, Sonogashira coupling, Heck coupling, or Hiyama coupling.

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