Imidazole alkynyl sulfur reagent, synthesis method thereof and application of imidazole alkynyl sulfur reagent in selective construction of thioglycoside compounds

Abstract

The invention discloses an imidazole alkynyl sulfur reagent as well as a synthesis method and application thereof in selective construction of thioglycoside, and the method comprises the following steps: taking brominated imidazole sulfosalt shown in a formula (1) as a reaction raw material, and reacting with alkyne shown in a formula (2) in an organic solvent to obtain the imidazole alkynyl sulfur reagent shown in a formula (3); a carbohydrate compound as shown in a formula (4) and an imidazole alkynyl sulfur reagent as shown in a formula (3) are used as reaction raw materials and react in an organic solvent under the action of alkali to obtain the thioglycoside compound as shown in a formula (5). The method has the advantages of mild reaction conditions, cheap and easily available raw materials, simple reaction operation, and high yield and selectivity; reaction substrates are easy to prepare; the reaction disclosed by the invention can be used for constructing a novel imidazole alkynyl sulfur reagent and a thioglycoside compound, and has wide application prospect and practical value.

Description

Technical Field

[0001] The invention belongs to the technical field of organic compound process application, and particularly relates to an imidazole alkynyl sulfide reagent and a synthesis method thereof, and application thereof in the selective construction of glucosidoglycoside compounds. Background Art

[0002] Glucosides are widely found in natural products and pharmaceuticals, and their synthesis has long attracted considerable attention. While scientists have devised a variety of glycosylation methods, existing preparation methods share a common drawback: they require pre-functionalization of the raw materials and require a multi-step synthesis catalyzed by transition metals, resulting in lengthy, time-consuming, and reagent-intensive synthetic routes.

[0003] Therefore, it is particularly important to find a universal, efficient, environmentally friendly, mild and economical method for synthesizing glucosinolates. Summary of the Invention

[0004] To overcome the limitations of traditional glucosinolate synthesis, the present invention uses imidazolyl alkynyl sulfide reagents to synthesize glucosinolates. This reaction is highly efficient and selective, requiring no pre-functionalization of the reaction substrate or the presence of a transition metal. It directly utilizes readily available raw materials to yield diverse, stereospecific glucosinolates. In light of this, the present invention proposes a reaction method for preparing an imidazolyl alkynyl sulfide reagent by reacting an alkynyl metal reagent with another molecule of imidazolethiourea. The present invention also proposes a reaction method for preparing a glucosinolate by reacting an imidazolyl alkynyl sulfide reagent with another molecule of a carbohydrate compound in the presence of a base.

[0005] The present invention provides an imidazolyl alkynyl sulfide reagent compound, the structural formula of which is shown in formula (3):

[0006]

[0007] Among them, R 1 Selected from hydrogen, benzene ring, substituted benzene ring, heteroaromatic ring, alkyl, active molecule; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ether-substituted phenyl, amino-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene; the active molecule is selected from adamantane, naproxen, telmisartan, isoxetine, opsazone, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, bezafibrate, estrone.

[0008] Preferably, R 1Selected from hydrogen, benzene ring, substituted benzene ring, heteroaromatic ring, C4-C33 alkyl, heteroatom-containing alkyl, active molecule; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ether-substituted phenyl, amino-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene; the active molecule is selected from adamantane, naproxen, telmisartan, isoxetine, opsazine, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, bezafibrate, estrone.

[0009] More preferably, R 1 Selected from hydrogen, benzene ring, substituted benzene ring, heteroaromatic ring, cyclopropyl, n-hexyl, 1-chloropropyl, pentenyl methyl ether, ethanol, acetal, cyclohexanol, oxacyclohexanol, active molecule; wherein the substituted benzene ring is selected from fluorine-substituted phenyl, methyl-substituted phenyl, pentenyl methyl ether substituted phenyl, amino-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene; the active molecule is selected from adamantane, naproxen, telmisartan, isoxetine, opsaqin, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, bezafibrate, estrone.

[0010] Furthermore, the imidazolyl alkynyl sulfide reagent compound represented by formula (3) of the present invention includes:

[0011]

[0012]

[0013] The present invention also provides a method for synthesizing an imidazole alkynyl sulfide reagent, wherein a bromoimidazolium sulfide salt represented by formula (1) is used as a reaction raw material, and reacts with an alkyne represented by formula (2) in an organic solvent under the action of an activating reagent and NaSbF6 to obtain an imidazole alkynyl sulfide reagent represented by formula (3). The reaction process is shown in reaction formula (a):

[0014]

[0015] Among them, R 1 The definition of is the same as that described in formula (3).

[0016] In the present invention, in reaction formula (a), the activating reagent is selected from one or more of zinc bromide, zinc chloride, n-butyl lithium, etc.; preferably, zinc bromide and n-butyl lithium.

[0017] In the present invention, in reaction formula (a), the organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, toluene, n-hexane, etc.; preferably, it is tetrahydrofuran.

[0018] In the present invention, in reaction formula (a), the reaction temperature is -78 to 25°C; preferably, -78°C.

[0019] In the present invention, in reaction formula (a), the reaction time is 1-16 hours; preferably, it is 2 hours.

[0020] In the present invention, in reaction formula (a), the amount ratio of the bromoimidazole sulfonate represented by formula (1), the alkyne represented by formula (2), the activation reagent, NaSbF6 and the organic solvent is 1 mol: (1-3) mol: (2-5) mol: (2-5) mol: (5-10) volume; preferably, it is 1 mol: 1 mol: 3 mol: 3 mol: 10 volume.

[0021] In the present invention, in reaction formula (a), the reaction is carried out in a nitrogen atmosphere.

[0022] The present invention also proposes the use of the imidazole alkynyl sulfide reagent in the selective construction of glucosidic compounds, wherein the saccharide compound represented by formula (4) and the imidazole alkynyl sulfide reagent represented by formula (3) are used as reaction raw materials, and under the action of a base, in an organic solvent, a glucosidic compound represented by formula (5) is obtained by reaction, and the reaction process is shown in reaction formula (b):

[0023]

[0024] Among them, R 1 The definition is the same as that described in formula (3); R is selected from benzyl, acyl, alkyl, and silicon; n is selected from an integer of 1-100; preferably, R is selected from benzyl, alkylacyl, alkyl, and silicon; n is selected from an integer of 1-10; further preferably, R is selected from benzyl, acetyl, alkyl, and silicon; n is selected from an integer of 4-6.

[0025] In the present invention, in reaction formula (b), the base is selected from one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide monohydrate, pyridine, 2,6-lutidine, 2,4,6-trimethylpyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), tetramethylguanidine (TMG), 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), etc.; preferably, it is one or two of 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), cesium hydroxide monohydrate, etc.

[0026] In the present invention, in reaction formula (b), the organic solvent is selected from one or more of dichloromethane, toluene, tetrahydrofuran, nitromethane, toluene, chloroform, acetone, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, ethyl acetate, etc.; preferably, it is acetone.

[0027] In the present invention, in reaction formula (b), the reaction temperature is -78 to 50°C; preferably, 25°C.

[0028] In the present invention, in reaction formula (b), the reaction time is 8-24 hours; preferably, 16 hours.

[0029] In the present invention, in reaction formula (b), the ratio of the carbohydrate compound, the base, the imidazole alkynyl sulfide reagent and the organic solvent is 1 mol: (1.5-3.1) mol: (1.5-3) mol: (5-10) volume; preferably, it is 1 mol: 1.5 mol: 2 mol: 10 volume.

[0030] In the present invention, in reaction formula (b), the reaction is carried out in an air atmosphere.

[0031] The present invention also provides a glucosidoglycoside compound, the structural formula of which is shown in formula (5):

[0032]

[0033] Wherein, the definition of R is the same as that described in reaction formula (b); R 1 The definition of is the same as that described in formula (3); n is selected from an integer of 1-100; preferably, n is selected from an integer of 1-10; further preferably, n is selected from an integer of 4-6.

[0034] Furthermore, the glucosinolate compounds represented by formula (5) of the present invention are shown in Table 2.

[0035] The present invention also proposes the use of the glucosinolate compound in the construction of a glucosinolate derivative. The glucosinolate compound shown in formula (5) is used as a reaction raw material. Under the action of an activation reagent, a glucosinolate derivative shown in formula (6) is obtained by reaction in an organic solvent. The reaction process is shown in reaction formula (c):

[0036]

[0037] Wherein, the definition of R is the same as that described in reaction formula (b); R 1 The definition of is the same as that in formula (3); R 2 Selected from primary alkyl, substituted olefin; n is selected from integers of 1-100;

[0038] Preferably, R 2is selected from a primary alkyl group and a substituted olefin; wherein the primary alkyl group is selected from a C8 alkyl group, and the substituted olefin is selected from a C8-C12 olefin; and n is an integer selected from 1 to 10;

[0039] More preferably, R 2 is selected from primary alkyl and substituted olefin; wherein the primary alkyl is selected from α-acetophenone, and the substituted olefin is selected from styrene, borate-substituted styrene, cyano and chlorine-substituted styrene; and n is selected from an integer of 4-6.

[0040] In the present invention, in reaction formula (c), the ratio of the glucosinolate compound represented by formula (5), the activation reagent and the organic solvent is 1 mol: (1-3) mol: (5-10) volume; preferably, it is 1 mol: 2 mol: 10 volume.

[0041] In the present invention, in reaction formula (c), the organic solvent is selected from one or more of n-hexane, tetrahydrofuran, toluene, 1,2-dichloroethane, etc., preferably, one or more of n-hexane, tetrahydrofuran, etc.;

[0042] In the present invention, in reaction formula (c), the activating reagent is selected from one or more of DIBAL-H (diisobutylaluminum hydride), n-butyllithium, borate, hydrogen peroxide, etc., preferably, one or more of DIBAL-H, n-butyllithium, etc.

[0043] In the present invention, in reaction formula (c), the reaction temperature is 0-80°C; preferably, 80°C.

[0044] In the present invention, in reaction formula (c), the reaction time is 0.5-3 hours; preferably, 1 hour.

[0045] The present invention also provides a glucosinolate derivative, the structural formula of which is shown in formula (6):

[0046]

[0047] Wherein, the definition of R is the same as that described in reaction formula (b); R 2 The definition is the same as that described in reaction formula (c); n is selected from an integer of 1-100; preferably, n is selected from an integer of 1-10; further preferably, n is selected from an integer of 4-6.

[0048] Furthermore, the glucosinolate derivatives represented by formula (6) of the present invention are shown in Table 3.

[0049] In a specific embodiment, the synthesis reaction of the present invention is carried out in a reaction bottle A, and a brominated imidazole salt (10 mmol) represented by formula (1), an alkyne (10 mmol) represented by formula (2), zinc bromide (20 mmol), n-butyl lithium (15 mmol), NaSbF6 (30 mmol), and an organic solvent (100 mL) are added to a reaction bottle B, and the reaction system is stirred at -78-25° C. under a nitrogen atmosphere for 3 hours; after the reaction is completed, silica gel is added and dried in a spin-drying manner, and the target product, i.e., an imidazole alkynyl sulfide reagent compound represented by formula (3), is obtained by column chromatography.

[0050] In another specific embodiment, the synthesis reaction of the present invention is carried out in a reaction flask B, and a carbohydrate compound (0.2 mmol) represented by formula (4), an imidazole alkynyl sulfide reagent (0.3 mmol) represented by formula (3), a base (0.4 mol), and an organic solvent (2 mL) are added to the reaction flask B, and the reaction system is stirred at 25° C. under an air atmosphere for 16 hours; after the reaction is completed, silica gel is added and dried, and the target product, i.e., a glucosidic compound represented by formula (5), is obtained by column chromatography.

[0051] In another specific embodiment, the synthesis reaction of the present invention is carried out in a reaction flask C, and a glucosinolate compound (0.1 mmol) represented by formula (5), an activation reagent (0.2 mmol), and an organic solvent (1 mL) are added to the reaction flask C, and the reaction system is stirred at 0-80° C. in an air atmosphere for 0.5-3 hours; after the reaction is completed, silica gel is added and dried, and the target product, i.e., a glucosinolate compound derivative represented by formula (6), is obtained by column chromatography.

[0052] The present invention also provides an imidazole alkynyl sulfide reagent compound as shown in formula (3) prepared according to the above-mentioned synthesis method of the present invention.

[0053] The present invention also proposes the use of the imidazolyl alkynyl thio reagent compound represented by formula (3) in the selective preparation of glucosidoglycoside compounds.

[0054] The present invention also proposes the use of the glucosinolate compound represented by formula (5) in the preparation of glucosinolate compound derivatives.

[0055] The yields of the imidazole alkynyl sulfide reagent compound represented by formula (3) and the glucosinolate compound represented by formula (5) prepared by the synthesis method of the present invention are 40% or more, and the yield of the glucosinolate compound derivative represented by formula (6) is 59% or more.

[0056] The present invention has the following advantages: no pre-functionalization of raw materials is required, no metal catalysis is required, raw materials are inexpensive and readily available, reaction substrates are easy to prepare, the reaction operation is simple, the reaction is efficient, and the yield is high. The imidazole alkynyl sulfide reagent is simple to prepare, stable, and has no irritating odor; and the reaction conditions are relatively mild. The imidazole alkynyl sulfide reagent of the present invention reacts with a carbohydrate compound to produce a glucosinolate compound. The reaction operation is simple, the reaction conditions are relatively mild, and the compound can be used to construct a novel glucosinolate compound, making it suitable for large-scale industrial production. DETAILED DESCRIPTION

[0057] The present invention will be further described in detail with reference to the following specific examples, and the protection content of the present invention is not limited to the following examples. Without departing from the spirit and scope of the inventive concept, changes and advantages that can be thought of by those skilled in the art are included in the present invention, and the scope of protection is based on the appended claims. The process, conditions, reagents, experimental methods, etc. for implementing the present invention, except for the contents specifically mentioned below, are all common knowledge and common common sense in the art, and the present invention does not particularly limit the content.

[0058] Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all of them. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention, its application, or use. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are intended to fall within the scope of protection of the present invention.

[0059] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not limiting. Therefore, other examples of the exemplary embodiments may have different values.

[0060] The present invention discloses an imidazole alkynyl sulfide reagent, a synthesis method thereof, and an application thereof in the selective construction of glucosinolates. The method uses a bromoimidazolyl sulfide salt represented by formula (1) as a reaction raw material, and reacts with an alkyne represented by formula (2) in an organic solvent to obtain an imidazole alkynyl sulfide reagent represented by formula (3); and uses a saccharide compound represented by formula (4) and an imidazole alkynyl sulfide reagent represented by formula (3) as reaction raw materials, and reacts in an organic solvent under the action of a base to obtain a glucosinolate compound represented by formula (5). The present invention has mild reaction conditions, cheap and readily available raw materials, simple reaction operation, high yield and selectivity, and easy preparation of reaction substrates. The reaction of the present invention can be used to construct novel imidazole alkynyl sulfide reagents and glucosinolate compounds, and has broad application prospects and practical value.

[0061] The data given in the following examples include specific operation and reaction conditions and products. The purity of the products was determined by nuclear magnetic resonance.

[0062] The synthesis reaction of the imidazole alkynyl sulfide reagent and the glucosidic compound of the present invention comprises the following steps:

[0063] As shown in reaction formula (a), the synthesis reaction of the present invention is to add the bromoimidazole salt shown in formula (1), the activating reagent, NaSbF6, the alkyne shown in formula (2), and the solvent into a reaction flask A, and stir the reaction system at -78-25°C under a nitrogen atmosphere for 3 hours; after the reaction is completed, silica gel is added and dried by spin drying, and the target product, i.e., the imidazole alkynyl sulfide reagent compound shown in formula (3), is obtained by column chromatography separation.

[0064] As shown in reaction formula (b), the synthesis reaction of the present invention is to add the carbohydrate compound represented by formula (4), the imidazole alkynyl sulfide reagent represented by formula (3), a base, and an organic solvent into a reaction flask B, and stir the reaction system at 25° C. in an air atmosphere for 16 hours; after the reaction is completed, silica gel is added and dried, and the target product, i.e., the glucosidic compound represented by formula (5), is obtained by column chromatography separation.

[0065] As shown in reaction formula (c), the synthesis reaction of the present invention is to add the glucosinolate compound represented by formula (5), an activation reagent, and a solvent into a reaction flask C, and stir the reaction system at 0-80° C. in an air atmosphere for 0.5-3 hours; after the reaction is completed, silica gel is added and dried, and the target product, i.e., the glucosinolate compound derivative represented by formula (6), is obtained by column chromatography separation.

[0066] The imidazolyl alkynyl sulfide reagent compounds shown in Table 1 are all products synthesized by the method of the present invention. There is no public document that discloses these compounds.

[0067] Table 1 New imidazolyl alkynyl sulfide reagent compounds of the present invention

[0068]

[0069]

[0070] The glucosinolate compounds shown in Table 2 are all products synthesized by the method of the present invention, and no public literature has disclosed these compounds.

[0071] Table 2 New glucosinolate compounds of the present invention

[0072]

[0073]

[0074]

[0075] The glucosinolate derivative compounds shown in Table 3 are all products synthesized by the method of the present invention, and no public literature has disclosed these compounds.

[0076] Table 3 New glucosinolate derivative compounds of the present invention

[0077]

[0078] Example 1

[0079]

[0080] To a reaction tube was added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (238.45 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr2 (225.19 mg, 1 mmol, 1 equiv), NaSbF6 (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3v as a white solid (665.2 mg, 96%). 1 H NMR (400MHz, CDCl3) δ2.98(s,3H),2.86(s,3H),1.79(m,2H),1.68(s,12H),1. 62(m,4H),1.56–1.43(m,2H),1.31(m,2H),0.87(s,9H),0.17(m,J=0.5Hz,6H). 13 C NMR (101MHz, CDCl3) δ138.5,138.3,138.1,86.6,85.7,80.4,79.9,41.2,26.0,25.3,22.8,18.2,-2.6,-2.7.IR( neat,cm-1)2906,2882,2206,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd for C 25 H 45 N2OSSi 449.7925,Found449.7910.

[0081] Example 2

[0082]

[0083] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (240.42 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr2 (225.19 mg, 1 mmol, 1 equiv), NaSbF6 (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3w (643.6 mg, 91%) as a white solid. 1 H NMR (400MHz, CDCl3) δ2.98(s,3H),2.86(s,3H),1.79(m,2H),1.68(s,12H),1.62(m,4H),1.56–1.43(m,2H),0.87(s,9H),0.17(m,J=0.5Hz,6H). 13 CNMR(101MHz, CDCl3)δ138.5,138.3,138.1,86.6,85.7,80.4,79.9,41.2,26.0,25.3,22.8,18.2,-2.6,-2.7.IR( neat,cm-1)2906,2882,2206,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd for C 24 H 43 N2O2SSi 451.7645,Found451.7639.

[0084] Example 3

[0085]

[0086] To a reaction tube was added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (240.42 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr2 (225.19 mg, 1 mmol, 1 equiv), NaSbF6 (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3x (708.05 mg, 92%) as a white solid. 1H NMR(400MHz, CDCl3)δ7.72(d,J=7.3Hz,4H),7.49–7.34(m,2H),7.33–7.27(m,4H) ,2.98(s,3H),2.86(s,3H),1.79(m,2H),1.68(s,12H),1.10(s,9H),0.18(m,6H). 13 C NMR (101MHz, CDCl3) δ146.7,138.7,138.2,138.1,138.0,128.6,128.5,128.3,128.2,128.1,128.0,127.8,127.7,127.6,127 .4,126.5,126.4,100.1,86.5,85.9,80.4,79.9,77.6,76.6,76.0,75.6,75.5,75.2,73.7,68.9,26.2,18.6,-3.0.IR(neat,cm -1 )2904,2882,2209,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd for C 32 H 45 N2SSiO 533.8695,Found 533.8693.

[0087] Example 4

[0088]

[0089] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (126.16 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr (225.19 mg, 1 mmol, 1 equiv), NaSbF (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was evaporated to dryness and column chromatography afforded 3y (504.46 mg, 88%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.45(m,2H),7.26–7.22(m,2H),2.98(s,3H),2.86(s,3H),1.79(m,2H),1.68(s,12H),3.61(m,1H),3.21(s,1H). 13C NMR (101MHz, CDCl3) δ138.3,138.0,137.9,96.2,86.4,85.6,83.3,80.4,80.2,68.9,26.2,18.6.IR(neat,cm -1 )3302,2904,2880,2209,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd for C 21 H 25 N2S 337.5045,Found 337.5029.Mp:105.2-106.1℃.

[0090] Example 5

[0091]

[0092] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (417.62 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr2 (225.19 mg, 1 mmol, 1 equiv), NaSbF6 (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The reaction was allowed to react at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3z (778.25 mg, 90%) as a white solid. 1 H NMR(400MHz, CDCl3)δ7.70–7.67(m,4H),7.62–7.59(m,4H),7.20–7.15(m,2H),2.98(s,3H),2.86(s,3H), 1.79(m,2H),1.68(s,12H),0.96(s,9H),0.95(s,9H),0.22(s,3H),0.19(s,3H),0.17(s,3H),0.17(s,3H). 13 C NMR (101MHz, CDCl3) δ163.1,145.2,138.5,138.4,138.2,138.1,138.0,137.9,134.9,132.3,98.5,9 8.1,86.4,85.5,80.4,80.2,68.6,62.8,35.5,29.7,25.9,23.9,18.2,-4.3,-4.4,-5.0.IR(neat,cm -1)2904,2886,2208,1498,1476,1362,1238,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd for C 37 H 50 O2N3SSi 628.9705,Found 628.9701.

[0093] Example 6

[0094]

[0095] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (354.57 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr2 (225.19 mg, 1 mmol, 1 equiv), NaSbF6 (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3aa (681.41 mg, 85%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.69–7.58(m,5H),7.05(m,1H),3.53–3.40(m,3H),2.98(s,3H),2.86(s,3H),1.79 (m,2H),1.68(s,12H),1.45(m,6H),0.88(s,9H),0.81(s,6H),0.03(s,5H),-0.05(s,3H),-0.11(s,2H). 13 C NMR (101MHz, CDCl3) δ157.3,157.2,138.6,138.5,138.3,138.2,127.3,126.8,126.5,126.4,8 0.0,79.9,79.6,55.2,46.8,25.9,25.8,18.2,18.1,16.7,16.5,-4.5,-5.2,-5.3.IR(neat,cm -1 )2908,2884,2209,1498,1480,1358,1234,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd forC 33 H 49 O2SSiN2565.9115,Found 565.9111.

[0096] Example 7

[0097]

[0098] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (354.57 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr (225.19 mg, 1 mmol, 1 equiv), NaSbF (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3ab (723.12 mg, 88%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.24–7.20(m,2H),7.06(d,J=7.5Hz,1H),6.71(d,J=7.5Hz,2H),2.98(s,3H),2.86(s,3H),2.35(s,6H),2.25(s,6 H),1.88–1.78(m,4H),1.79(m,2H),1.68(s,12H),1.67–1.54(m,4H),0.99(s,10H),0.97(s,9H),0.26(s,3H),0.23(s,3H),0.17(m,6H). 13 C NMR (101MHz, CDCl3) δ157.2,128.5,128.4,128.3,128.0,127.9,127.8,127.7,123.7,120.7,112.1,80. 6,80.3,39.3,39.3,34.6,34.5,25.9,24.4,23.2,23.1,21.5,18.3,15.9,-3.9,-4.0,-5.1.IR(neat,cm -1 )2902,2880,2202,1497,1478,1359,1236,1136,1060,1039,732,694.HRMS(ESI)m / z:[M]+Calcd forC 34 H 57 O2SSiN2585.9865,Found585.9866.

[0099] Example 8

[0100]

[0101] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (290.52 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr (225.19 mg, 1 mmol, 1 equiv), NaSbF (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The reaction was allowed to react at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3ac (604.85 mg, 82%) as a white solid. 1 H NMR(400MHz, CDCl3)δ2.98(s,3H),2.86(s,3H),2.20(m,4H),1.92(s,2H),1.78–1 .62(m,6H),1.68(s,12H),1.49(dd,J=12.4,2.6Hz,2H),0.92(s,9H),0.20(m,6H). 13 C NMR (101MHz, CDCl3) δ157.2,128.5,128.4,86.5,69.0,40.0,38.0,35.4,35.3,31.9,27.0,26.9,26.2,18.6,-2.6.IR(neat,cm -1 )2904,2880,2203,1498,1482,1358,1234,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd forC 29 H 49 OSSiN2501.8685,Found 501.8682.

[0102] Example 9

[0103]

[0104] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (290.52 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr (225.19 mg, 1 mmol, 1 equiv), NaSbF (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3ad (879.68 mg, 81%) as a white solid. 1H NMR(400MHz, CDCl3)δ8.03(dd,J=7.3,2.6Hz,1H),7.98–7.91(m,1H),7.71(m,1H) ),7.60(d,J=5.3Hz,1H),7.40–7.33(m,3H),7.31–7.24(m,3H),5.61(d,J=7.4Hz, 2H),5.19–4.95(m,5H),2.98(s,6H),2.86(s,3H),2.13–2.00(m,2H),1.68(s,12H ),1.29–1.21(m,4H),0.94(s,9H),0.11(d,J=5.2Hz,3H),-0.01(d,J=4.3Hz,3H). 13 C NMR (101MHz, CDCl3) δ156.8,143.4,140.1,139.7,139.6,138.2,138.1,138.0,136.3,135.2,127.9,127 .6,126.0,68.7,68.5,62.9,47.0,31.9,29.9,25.7,21.8,18.1,17.0,14.2,-4.5,-4.6,-5.IR(neat,cm -1 )2904,2880,2207,1498,1362,1238,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd for C 52 H 65 N6SOSi 850.2775,Found850.2769.

[0105] Example 10

[0106]

[0107] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (410.67 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr2 (225.19 mg, 1 mmol, 1 equiv), NaSbF6 (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3ae (686.22 mg, 80%) as a white solid. 1H NMR (400MHz, CDCl3) δ7.44–7.09(m,1H),6.68–6.54(m,2H),2.98(s,6H),2.89–2.75(m,2H),2.68(m,1H),2.44–2.25(m,4H),2.00(t, J=11.8Hz,2H),1.91–1.69(m,5H),1.68(s,12H),1.47(m,1H),1.33–1.27(m,2H),0.95(s,9H),0.89(s,3H),0.27(s,3H),0.24(s,3H). 13 C NMR (101MHz, CDCl3) δ153.5,138.0,137.9,132.7,128.5,128.4,128.3,86.5,49.0,43.7, 40.3,39.6,33.1,31.6,30.2,29.7,27.3,26.5,26.0,23.2,18.3,13.3,-2.8.IR(neat,cm -1 )2900,2878,2202,1498,1479,1359,1236,1136,1060,1028,732,694.HRMS(ESI)m / z:[M]+Calcd for C 37 H 57 O2SSiN2622.0195,Found 622.0192.

[0108] Example 11

[0109]

[0110] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (278.40 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr (225.19 mg, 1 mmol, 1 equiv), NaSbF (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 h. After completion, the reaction was dried and purified by column chromatography to afford 3af (660.20 mg, 91%) as a white solid. 1H NMR(400MHz, CDCl3)δ7.45(d,J=7.2Hz,2H),7.25–7.16(m,1H),2.98(s,6H),2.89–2.76(m,2H) ),2.38(m,2H),2.24–1.87(m,4H),1.65(m,12H),1.00(d,J=7.2Hz,1H),0.94(d,J=1.4Hz,3H). 13 C NMR (101MHz, CDCl3) δ141.5,127.9,127.8,127.5,125.4,124.5,86.5,50.5,49.7,48.0,46.7,44.5,44.4,39.3,38.0,36.6,35.9, 34.9,34.6,34.4,31.7,31.6,31.5,30.3,29.8,29.3,29.1,27.3,26.3,26.1,25.9,25.6,23.7,23.5,21.6,14.4,13.9.IR(neat,cm -1 )2904,2882,2204,1498,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M]+Calcd for C 31 H 41 OSN2489.7415,Found489.7408.

[0111] Example 12

[0112]

[0113] To a reaction tube was added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (278.40 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr2 (225.19 mg, 1 mmol, 1 equiv), NaSbF6 (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was dried and purified by column chromatography to afford 3ag (689.37 mg, 86%) as a white solid. 1H NMR(501MHz, CDCl3)δ2.98(s,6H),2.83–2.73(m,1H),2.41–2.33(m,2H),2.30–2.25(m,1H),2.12(s,3H),1.97(m,1H),1.85–1.76(m, 3H),1.68(s,12H),1.66–1.55(m,4H),1.44(dd,J=13.1,3.6Hz,1H),1.34(m,2H),1.18(s,3H),1.04(s,3H),1.01(m,1H),0.88(m,1H). 13 C NMR (126MHz, CDCl3) δ208.1,199.4,81.8,53.0,47.0,38.5,35.7,35.6,33.9,33.6,32.9,32.7,31.5,27.0,24.6,21.1,20.7,17.4,14.9.IR(neat,cm -1 )2906,2882,2206,1746,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(EI)m / z:[M]+Calcd for C 34 H 49 O3SN2565.8365,Found 565.8360.Mp:119.6-121.3℃.

[0114] Example 13

[0115]

[0116] To a reaction tube were added imidazolium bromide (372.16 mg, 1 mmol, 1 equiv), alkyne (278.40 mg, 1 mmol, 1 equiv), n-BuLi (1 mL, 1 mmol, 1 equiv), ZnBr2 (225.19 mg, 1 mmol, 1 equiv), NaSbF6 (776.22 mg, 3 mmol, 3 equiv), and THF (10 mL). The mixture was reacted at -78°C for 2 hours. After completion, the reaction was evaporated to dryness and column chromatography afforded 3ah (879.36 mg, 89%) as a white solid. 1H NMR (501MHz, CDCl3) δ5.29(d,J=1.4Hz,1H),5.15(d,J=3.0Hz,1H),2.98(s,6H),2.30–2.11(m,3H),2.01–1.90(m,2H),1.83– 1.59(m,22H),1.43–1.10(m,7H),0.99(s,3H),0.96(s,9H),0.91(s,9H),0.87(s,3H),0.22(s,3H),0.19(s,4H),0.16(m,6H). 13 C NMR (126MHz, CDCl3) δ150.4,101.7,86.5,85.5,50.4,48.5,48.2,40.3,34.9,34.1,33.0,32 .7,31.6,27.7,25.9,25.7,23.5,21.0,19.1,18.3,18.1,13.3,-2.9,-4.1,-4.4.IR(neat,cm -1 )2904,2880,2208,1498,1479,1358,1234,1136,1062,1039,732,694.HRMS(ESI)m / z:[M]+Calcd for C 44 H 75 O2N2SSi2752.3255,Found 752.3250.

[0117] Example 14

[0118]

[0119] A saccharide (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5a as a white solid (126.1 mg, 96%). 1 H NMR (400MHz, CDCl3) δ7.50 (m, 4H), 7.46–7.27 (m, 21H), 5.17 (d, J = 10.2Hz, 1H), 5.08–4. 90(m,4H),4.73(m,3H),4.51(d,J=9.2Hz,1H),4.00–3.80(m,5H),3.65(d,J=3.4Hz,1H). 13C NMR (101MHz, CDCl3) δ138.4,138.2,138.1,132.0,128.6,128.5,128.4,128.1,128.0,127.9,12 7.6,123.1,96.8,86.5,85.7,80.4,80.2,77.7,76.0,75.7,75.3,74.9,73.6,68.6.IR(neat,cm -1 )2902,2866,2209,1496,1479,1467,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 40 O5SNa 679.2494,Found 679.2484.Mp:60.5–61.7℃.

[0120] Example 15

[0121]

[0122] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (169.0 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded the colorless liquid 5b (123.4 mg, 92%). 1 H NMR(500MHz, CDCl3)δ7.47(d,J=6.8Hz,2H),7.35m,18H),7.24(dd,J=7.4,1.9Hz,2H),7 .11(d,J=8.0Hz,2H),5.13(d,J=10.2Hz,1H),4.98(d,J=10.9Hz,1H),4.95–4.86(m,3H), 4.74(d,J=12.1Hz,1H),4.65(dd,J=16.1,11.4Hz,2H),4.45(d,J=9.3Hz,1H),3.93–3.88 (m,1H),3.86–3.83(m,2H),3.78(dd,J=6.7,2.8Hz,2H),3.62–3.58(m,1H),2.38(s,3H). 13C NMR (126MHz, CDCl3) δ138.9,138.4,138.3,138.1,138.0,132.0,129.1,128.6,128.5,128.4,128.0,127.9,1 27.8,127.5,120.0,96.9,86.5,85.7,80.3,80.2,77.6,76.0,75.7,75.2,73.9,73.6,68.6,21.6.IR(neat,cm -1 )2900,2862,2360,1508,1452,1355,1276,1261,1132,1083,1056,1028,989,763,750,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 43 H 46 O5SNa 697.2964,Found697.2947.

[0123] Example 16

[0124]

[0125] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (173.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and purified by column chromatography to afford 5c as a white solid (116.8 mg, 85%). 1 H NMR (400MHz, CDCl3) δ7.55–7.51(m,2H),7.46–7.34(m,18H),7.31–7.28(m,2H),6.89–6.83(m,2H),5.20(d,J=10.3Hz,1H),4.98(m,4H),4.80( d,J=12.0Hz,1H),4.70(dd,J=17.1,11.4Hz,2H),4.49(d,J=9.3Hz,1H),3.99–3.88(m,3H),3.85(s,4H),3.84–3.82(m,1H),3.69–3.61(m,1H). 13CNMR (101MHz, CDCl3) δ160.1,138.5,138.4,138.2,133.9,128.6,128.5,128.4,128.0,127.9,127.6,1 15.2,114.1,96.8,86.6,85.8,80.3,80.2,77.7,76.0,75.7,75.2,73.6,73.1,68.7,55.4.IR(neat,cm -1 )2902,2858,2201,1496,1479,1467,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 43 H 42 O6SNa 709.2600,Found709.2591.Mp:75.1–76.3℃.

[0126] Example 17

[0127]

[0128] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (199.3 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded a colorless liquid, 5d (131.2 mg, 85%). 1 H NMR(400MHz, CDCl3)δ7.47(dd,J=7.9,1.3Hz,2H),7.41–7.29(m,20H),7.26–7.22(m,2H),6.69(s,1H),5.13(d,J=10.3Hz,1H),5.02–4.85 (m,4H),4.68(m,3H),4.45(d,J=9.3Hz,1H),3.93–3.87(m,1H),3.84(d,J=2.9Hz,2H),3.82–3.74(m,2H),3.64–3.54(m,1H),1.57(s,9H). 13C NMR (101MHz, CDCl3) δ152.4,139.0,138.4,138.3,138.1,138.0,133.1,128.6,128.5,128.4,128.0,127.9,127.8,127 .6,118.1,117.2,96.6,86.5,85.8,81.0,80.3,80.1,77.7,77.4,75.9,75.7,75.2,73.8,73.6,68.6,28.4.IR(neat,cm -1 )2906,2866,2205,1485,1479,1467,1359,1236,1136,1060,1028,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 47 H 49 O7SNNa794.3127,Found794.3121.

[0129] Example 18

[0130]

[0131] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (185.2 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and reacted at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5e (114.5 mg, 79%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.48(q,J=8.7Hz,4H),7.42(m,2H),7.37–7.28(m,16H),7.25–7.22(m,2H),5.04(d,J=10.3Hz,1H),4.99–4 .86(m,4H),4.69(dd,J=14.8,11.4Hz,2H),4.60(d,J=12.0Hz,1H),4.48(d,J=8.8Hz,1H),3.86–3.76(m,5H),3.64–3.57(m,1H). 13C NMR (101MHz, CDCl3) δ138.2,138.2,138.0,137.8,131.7,128.6,128.5,128.4,128.3,128.1,128.0, 127.9,127.7,127.6,125.3,95.4,86.4,85.5,80.4,80.1,78.4,77.6,76.0,75.7,75.2,73.6,68.6. 19 FNMR(376MHz,CDCl3)δ-62.79(s).IR(neat,cm -1 )2904,2856,2212,1496,1479,1467,1236,1060,1039,1028,728,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 43 H 39 O5F3SNa747.2368,Found 747.2357.Mp:77.6–78.9℃.

[0132] Example 19

[0133]

[0134] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (180.0 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and reacted at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and purified by column chromatography to afford 5f (128.8 mg, 91%) as a white solid. 1 H NMR(400MHz, CDCl3)δ8.87(s,1H),8.07m,2H),7.71–7.58(m,2H),7.49(t,J=7.3Hz,1H),7.40(m,2H),7.34–7.22(m,12H),7.2 1–7.14(m,6H),5.05(d,J=10.3Hz,1H),4.95–4.79(m,4H),4.61(m,3H),4.48(d,J=9.2Hz,1H),3.87–3.70(m,5H),3.56(m,1H). 13C NMR (101MHz, CDCl3) δ152.0,146.8,138.7,138.3,138.2,138.0,137.9,130.3,129.4,128.6,128.5,128.4,128.1,128.0,127.9,1 27.8,127.7,127.6,127.4,127.2,117.2,94.0,86.5,85.8,80.5,80.2,79.2,77.6,77.4,76.0,75.7,75.2,73.6,68.6.IR(neat,cm -1 )2904,2868,2206,1498,1479,1467,1359,1236,1138,1062,1039,1028,738.HRMS(ESI)m / z:[M+H] + Calcd for C 45 H 42 O5SN 708.2784,Found 708.2774.Mp:80.6–82.1℃.

[0135] Example 20

[0136]

[0137] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (165.0 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5 g (114.5 mg, 87%) of a colorless liquid. 1 H NMR(400MHz, CDCl3)δ8.55(d,J=4.2Hz,1H),7.55(td,J=7.8,1.8Hz,1H),7.39(m,2H),7.36–7.26(m,18H),7.21–7.18(m,2H) ,5.03(d,J=10.3Hz,1H),4.89(m,5H),4.64(m,3H),4.51(d,J=9.3Hz,1H),3.87–3.80(m,3H),3.79–3.74(m,2H),3.59(m,1H). 13C NMR (101MHz, CDCl3) δ149.7,142.9,138.3,138.0,137.8,136.2,128.5,128.4,128.3,128.0,127.9,12 7.8,127.5,127.0,122.7,96.1,86.4,85.7,80.4,80.1,77.5,75.9,75.7,75.2,73.6,68.6.IR(neat,cm -1 )2902,2866,2209,1498,1482,1469,1359,1236,1136,1039,732.HRMS(ESI)m / z:[M+H] + Calcd for C 41 H 40 O5SN 658.2627,Found 658.2621.

[0138] Example 21

[0139]

[0140] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (172.0 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was dried and purified by column chromatography to afford 5h (91.2 mg, 67%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.45(m,2H),7.42–7.30(m,20H),7.26–7.22(m,2H),5.08(d,J=10.2Hz,1H),5.01–4.86(m,4 H),4.68(m,3H),4.47(d,J=9.1Hz,1H),3.90–3.82(m,3H),3.79(dd,J=6.7,2.6Hz,2H),3.61(m,1H),3.21(s,1H). 13 C NMR (101MHz, CDCl3) δ138.3,138.0,137.9,132.1,131.6,128.6,128.5,128.4,128.1,128.0,127.9,127.8,127. 6,123.5,122.1,96.2,86.4,85.6,83.3,80.4,80.2,79.2,77.6,77.4,76.0,75.7,75.2,73.6,68.6.IR(neat,cm-1 )3302,2904,2880,2209,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 44 H 40 O5SNa 703.2494,Found 703.2488.Mp:105.2–106.1℃.

[0141] Example 22

[0142]

[0143] A carbohydrate compound (194.6 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5i (165.5 mg, 76%) as a colorless liquid. 1 H NMR (500MHz, CDCl3) δ7.52(m,2H),7.47–7.29(m,36H),7.22m,2H),5.22(d,J=10.4Hz,1H),5.06(dd,J=26.7 ,10.5Hz,3H),4.89(dd,J=25.8,11.2Hz,2H),4.82(dd,J=11.6,3.2Hz,3H),4.74(d,J=12.0Hz,1H),4.63(dd ,J=20.7,9.6Hz,2H),4.51(dd,J=25.5,10.7Hz,2H),4.43(d,J=11.8Hz,1H),4.35(d,J=11.8Hz,1H),4.18(t ,J=9.4Hz,1H),4.05–3.98(m,2H),3.93–3.81(m,3H),3.75(t,J=9.0Hz,1H),3.68–3.62(m,1H),3.50(m,4H). 13C NMR (126MHz, CDCl3) δ139.2,138.9,138.8,138.6,138.5,138.3,138.2,1 32.0,128.6,128.5,128.4,128.3,128.2,128.0,127.9,127.8,127.7,12 7.6,127.5,127.4,102.7,85.8,84.8,82.7,80.5,80.2,79.7,76.0,75.9 ,75.8,75.5,74.9,73.8,73.5,73.2,73.1,72.7,68.1,67.9.IR(neat,cm -1 )2903,2882,2206,1497,1479,1359,1238,1136,1060,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 69 H 68 O 10 SNa 1111.4431,Found 1111.4417.

[0144] Example 23

[0145]

[0146] A carbohydrate compound (185.0 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5j (170.7 mg, 82%) as a colorless liquid. 11H NMR (400 MHz, CDCl3) δ 7.51–7.45 (m, 2H), 7.35–7.29 (m, 3H), 5.42–5.26 (m, 5H), 5.17 (t, J = 9.4 Hz, 1H), 5.06 (t, J = 9.9 Hz, 1H), 4.85 (dd, J = 10.5, 4.0 Hz, 1H), 4.74 (dd, J = 10.3, 4.1 Hz, 1H), 4.63 (d, J = 9.7 Hz, 1H), 4.47 (td, J = 12.4, 2.4 Hz, 2H), 4.31 (dd, J = 12.3, 4.3 Hz, 1H), 4.24 (dd, J = 12.5, 3.5 Hz, 1H), 4.16 (dd, J = 12.4, 3.4 Hz, 1H), 4.08–3.88 (m, 5H), 3.85–3.78 (m, 1H), 2.13 (m, 6H), 2.09 (s, 3H), 2.07 (s, 3H), 2.05 (s, 3H), 2.02 (m, 6H), 1.99 (m, 9H). 13 13C NMR (101 MHz, CDCl3) δ 170.7, 170.6, 170.5, 170.4, 170.2, 169.8, 169.7, 169.5, 1-69.4, 132.1, 128.9, 128.4, 122.6, 100.0, 97.2, 95.9, 95.7, 83.8, 77.2, 76.3, 73.5, 72.6, 72.5, 71.7, 70.6, 70.4, 70.1, 69.4, 69.1, 68.5, 67.9, 63.1, 62.3, 61.4, 20.9, 20.8, 20.7, 20.6. IR (neat, cm -1 ) 2906, 2882, 2206, 1758, 1689, 1496, 1479, 1359, 1236, 1136, 1060, 1039, 1028, 732, 694. HRMS (ESI) m / z: [M+Na] + Calcd for C 46 H 56 O 25 SNa 1063.2729, Found 1063.2725.

[0147] Example 24

[0148]

[0149] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (259.4 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5k (103.1 mg, 53%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.70–7.67(m,4H),7.62–7.59(m,4H),7.35(m,48H),7.20–7.15(m,4H), 5.03(d,J=10.2Hz,2H),4.98(d,J=11.0Hz,3H),4.94–4.80(m,8H),4.77(m,2H),4.72–4.52(m, 9H),4.42(t,J=4.4Hz,2H),3.85–3.67(m,13H),3.61–3.54(m,2H),3.09(t,J=7.6Hz,4H),2.3 8–2.27(m,5H),0.96(s,9H),0.95(s,9H),0.22(s,3H),0.19(s,3H),0.17(s,3H),0.17(s,3H). 13 C NMR (101MHz, CDCl3) δ163.1,145.2,138.5,138.4,138.2,138.1,138.0,137.9,134.9,132 .3,130.1,129.0,128.6,128.5,128.4,128.3,128.1,128.0,127.9,127.8,127.7,127.6, 126.5,98.5,98.1,86.4,85.5,80.4,80.2,79.9,77.7,77.6,75.8,75.7,75.6,75.1,73.5 ,70.9,70.7,68.7,68.6,62.8,35.5,29.7,25.9,23.9,18.2,-4.3,-4.4,-5.0.IR(neat,cm -1 )2904,2886,2208,1498,1476,1362,1238,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 60 H 66 O7SSiN 972.4329,Found 972.4327.

[0150] Example 25

[0151]

[0152] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (257.3 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was dried and column chromatography yielded 5 μl (140.9 mg, 73%) of a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.44–7.09 (m, 21H), 6.68–6.54 (m, 2H), 5.30 (s, 1H), 5.03 (d, J = 10.1Hz, 1H), 4. 92–4.79(m,3H),4.66(m,4H),4.37(d,J=9.4Hz,1H),3.90(t,J=8.9Hz,1H),3.81(s,2H),3.72(m,2H), 3.56(d,J=9.0Hz,1H),2.89–2.75(m,2H),2.68(m,1H),2.44–2.25(m,4H),2.00(t,J=11.8Hz,2H),1. 91–1.69(m,5H),1.47(m,1H),1.33–1.27(m,2H),0.95(s,9H),0.89(s,3H),0.27(s,3H),0.24(s,3H). 13 C NMR (101MHz, CDCl3) δ153.5,138.5,138.3,138.1,138.0,137.9,132.7,128.5,12 8.4,128.3,128.1,127.9,127.8,127.5,127.4,126.5,115.4,112.7,101.9,86.5 ,85.3,81.7,80.7,79.7,77.9,75.7,75.4,73.8,71.6,68.7,49.0,43.7,40.3,39 .6,33.1,31.6,30.2,29.7,27.3,26.5,26.0,23.2,18.3,13.3,-2.8.IR(neat,cm -1 )2900,2878,2202,1498,1479,1359,1236,1136,1060,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 60 H 72O7SSiNa 987.4666,Found987.4653.

[0153] Example 26

[0154]

[0155] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (170.2 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5m (125.5 mg, 93%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.41–7.37(m,2H),7.33–7.22(m,18H),7.17(m,2H),7.03–6.96(m,2H),5.07(d,J=10.3Hz,1H),4 .86(m,4H),4.61(m,3H),4.40(d,J=9.3Hz,1H),3.88(t,J=9.0Hz,1H),3.77(d,J=2.8Hz,2H),3.72(m,2H),3.54(m,1H). 13 C NMR (101MHz, CDCl3) δ164.4,161.9,138.5,138.4,138.1,133.7,130.3,130.2,128.6,128.5,128.4,128.0,127.9,1 27.8,127.7,127.6,124.0,115.7,115.5,111.9,111.7,90.1,86.5,85.6,80.3,77.7,75.9,75.7,75.2,73.6,68.6. 19 F NMR(376MHz,CDCl3)δ-108.92(s).IR(neat,cm -1 )2900,2864,2206,1482,1479,1467,1342,1236,1136,1060,1039,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 39 O5SFNa 697.2400,Found 697.2386.Mp:68.7–69.5℃.

[0156] Example 27

[0157]

[0158] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (169.0 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and purified by column chromatography to afford 5n (127.5 mg, 95%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.54–7.49(m,2H),7.42–7.28(m,20H),7.25–7.17(m,2H),5.17(d,J=10.3Hz,1H),5.07–4.90 (m,4H),4.83–4.77(m,1H),4.75–4.65(m,2H),4.49(d,J=9.3Hz,1H),4.00–3.79(m,5H),3.65(m,1H),2.35(s,3H). 13 C NMR (101MHz, CDCl3) δ138.4,138.2,138.1,132.5,129.6,129.1,128.6,128.5,128.4,128.3,128.0,127. 9,127.6,122.9,97.0,86.5,85.7,80.4,80.3,77.7,76.0,75.7,75.2,74.4,73.7,68.7,21.3.IR(neat,cm -1 )2904,2868,2205,1479,1467,1359,1236,1136,1060,1039,1028,738,696.HRMS(ESI)m / z:[M+Na] + Calcd for C 43 H 42 O5SNa 693.2651,Found 693.2641.Mp:48.7–49.3℃.

[0159] Example 28

[0160]

[0161] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (194.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5o (140.8 mg, 93%) as a colorless liquid. 1 H NMR (500MHz, CDCl3) δ7.54–7.50(m,3H),7.45–7.32(m,16H),7.28(m,2H),7.16(dd,J=8.2,1.7H z,1H),7.05(d,J=8.2Hz,1H),5.18(d,J=10.3Hz,1H),4.99(m,3H),4.92(d,J=10.8Hz,1H),4.77 (d,J=12.1Hz,1H),4.70(m,2H),4.50(d,J=9.3Hz,1H),3.94(t,J=9.0Hz,1H),3.88(d,J=2.8Hz, 2H),3.86–3.79(m,2H),3.64m,1H),3.13–3.02(m,2H),1.97(dd,J=7.1,5.1Hz,2H),1.33(m,6H). 13 C NMR (126MHz, CDCl3) δ142.1,138.5,138.3,138.2,138.1,133.9,130.3,129.7,128.6,128.5,128.1,127.9,127.7,126 .6,118.4,97.1,86.6,85.9,80.4,80.2,77.7,76.0,75.7,75.2,73.9,73.6,68.6,37.3,33.0,30.0,23.3.IR(neat,cm -1 )2902,2866,2212,1484,1479,1467,1359,1236,1128,1060,1039,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 47 H 48 O5S2Na 779.2841,Found 779.2837.

[0162] Example 29

[0163]

[0164] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (179.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5p (140.0 mg, 99%) as a white solid. 1 H NMR (400MHz, CDCl3) δ8.49(d,J=8.0Hz,1H),7.92(m,2H),7.76(dd,J=7.1,0.8Hz,1H),7.61–7.50(m,4H),7.50–7.30(m,19H),5.26(d,J =10.3Hz,1H),5.02(m,4H),4.77(m,3H),4.63(d,J=9.3Hz,1H),4.08(t,J=9.0Hz,1H),3.95(d,J=2.8Hz,2H),3.90(m,2H),3.73(m,1H). 13 C NMR (101MHz, CDCl3) δ138.5,138.3,138.2,138.1,133.7,133.3,130.8,129.1,128.6,128.6,128.5,128.4,128.1,128.0,127.9 ,127.7,127.1,126.6,126.4,125.3,120.8,95.1,86.6,85.9,80.5,80.3,79.8,77.7,76.0,75.8,75.3,73.7,68.7.IR(neat,cm -1 )2904,2868,2205,1496,1479,1467,1346,1226,1136,1060,1039,1028,738,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 46 H 42 O5SNa 729.2651,Found 729.2639.Mp:80.5–81.3℃.

[0165] Example 30

[0166]

[0167] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (194.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded the colorless liquid 5q (148.4 mg, 98%). 1 H NMR (400MHz, CDCl3) δ8.72 (m, 2H), 8.59 (dd, J = 8.1, 0.9Hz, 1H), 8.06 (s, 1H), 7.87 –7.82(m,1H),7.77–7.71(m,2H),7.69–7.62(m,2H),7.61–7.56(m,2H),7.49–7.3 7(m,13H),7.36–7.29(m,5H),5.29(d,J=10.3Hz,1H),5.03(m,4H),4.75(m,4H),4 .10(t,J=9.1Hz,1H),3.96(d,J=2.9Hz,2H),3.94–3.89(m,2H),3.80–3.69(m,1H). 13 C NMR (101MHz, CDCl3) δ138.5,138.3,138.2,138.1,132.3,131.4,131.2,130.5,130.2,128.8,128.6,128.5,128.1,127.9,127.7,1 27.3,127.2,127.1,122.9,122.7,119.6,95.2,86.6,86.0,80.6,80.3,79.6,77.8,77.5,76.0,75.8,75.3,73.8,68.8.IR(neat,cm -1 )2903,2868,2205,1496,1467,1349,1236,1136,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 50 H 44 O5SNa 779.2807,Found 779.2796.

[0168] Example 31

[0169]

[0170] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (166.6 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5r (122.0 mg, 92%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.36(m,2H),7.30–7.19(m,18H),7.13(dd,J=3.8,2.6Hz,2H),6.86(dd,J=5.2,3.7Hz,1H),4.99(d, J=10.3Hz,1H),4.82(m,5H),4.62(d,J=12.1Hz,1H),4.54(m,2H),4.35(d,J=9.2Hz,1H),3.80–3.62(m,6H),3.49(m,1H). 13 C NMR (101MHz, CDCl3) δ138.4,138.3,138.1,138.0,133.9,128.6,128.5,128.4,128.1,128.0,127.9,12 7.6,127.1,123.2,89.6,86.5,86.0,80.4,80.2,79.7,77.7,76.0,75.8,75.2,73.6,68.6.IR(neat,cm -1 )2904,2868,2209,1496,1458,1328,1209,1142,1060,1039,1028,732.HRMS(ESI)m / z:[M+Na] + Calcdfor C 40 H 38 O5S2Na 685.2058,Found 685.2052.

[0171] Example 32

[0172]

[0173] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (141.9 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5s (103.4 mg, 89%) as a colorless liquid. 1H NMR (400MHz, CDCl3) δ7.45–7.30(m,18H),7.25–7.21(m,2H),5.03(d,J=10.3Hz,1H),4.95(m,2H),4.88(dd,J=10.5,4.9 Hz,2H),4.76–4.67(m,2H),4.66–4.60(m,2H),4.42(d,J=9.2Hz,1H),3.89–3.71(m,5H),3.62–3.53(m,1H),3.01(s,1H). 13 C NMR (101MHz, CDCl3) δ138.4,138.3,138.0,137.9,128.5,128.4,128.0,127.9,127.8 ,127.6,86.4,86.0,85.2,80.1,77.6,75.9,75.6,75.2,73.6,70.3,68.6.IR(neat,cm -1 )3306,2902,2209,1498,1479,1467,1359,1236,1136,1060,1039,732.HRMS(ESI)m / z:[M+Na] + Calcd for C 36 H 36 O5SNa 603.2181,Found603.2172.

[0174] Example 33

[0175]

[0176] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (154.0 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5t (90.7 mg, 73%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.46–7.29(m,18H),7.26–7.22(m,2H),5.04(d,J=10.3Hz,1H),4.91(m,5H),4 .68(m,4H),4.31(d,J=8.9Hz,1H),3.86–3.73(m,5H),3.56(m,1H),1.38(m,1H),0.86–0.70(m,4H). 13CNMR (101MHz, CDCl3) δ137.4,137.1,127.6,127.5,127.4,127.0,126.9,126.8,126.6,101 .4,85.5,84.6,79.1,79.0,76.7,75.0,74.5,74.2,72.5,67.6,58.8,8.2,0.0.IR(neat,cm -1 )2904,2882,2210,1498,1467,1362,1236,1136,1060,1039,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 39 H 40 O5SNa 643.2494,Found 643.2486.

[0177] Example 34

[0178]

[0179] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (167.2 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5u (92.5 mg, 76%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.43–7.30(m,18H),7.25–7.20(m,2H),5.06(d,J=10.2Hz,1H ),4.93(dd,J=24.5,10.9Hz,2H),4.86(dd,J=10.5,3.2Hz,2H),4.67(m,4H),4.32( d,J=9.1Hz,1H),3.83–3.80(m,2H),3.77–3.72(m,2H),3.58–3.52(m,1H),2.34(t, J=7.1Hz,2H),1.58–1.49(m,2H),1.40(m,2H),1.29(m,4H),0.89(t,J=7.0Hz,3H). 13C NMR (101MHz, CDCl3) δ138.5,138.4,138.1,128.5,128.4,128.0,127.9,127.8,127.6,98.6,86.5,85.4 ,80.1,80.0,77.7,75.9,75.5,75.2,73.5,68.6,63.8,31.4,28.7,28.6,22.6,20.3,14.1.IR(neat,cm -1 )2900,2864,2205,1494,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 48 O5SNa 687.3120,Found 687.3105.

[0180] Example 35

[0181]

[0182] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.9 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5v (96.0 mg, 73%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.46–7.29(m,18H),7.23(dd,J=7.2,2.1Hz,2H),5.03(d,J=10.3Hz,1H),4.94(dd,J=22.4,11.0Hz,2H),4 .88(dd,J=10.5,2.1Hz,2H),4.66(m,3H),4.36(d,J=8.7Hz,1H),3.78(m,5H),3.61(m,3H),2.55(t,J=6.7Hz,2H),1.95(m,2H). 13C NMR (101MHz, CDCl3) δ138.4,138.3,138.1,138.0,128.5,128.4,128.3,128.0,127.9,127.8,127.7, 96.2,86.4,85.4,80.1,79.9,77.6,75.9,75.5,75.2,73.5,68.6,65.6,43.6,31.3,17.7.IR(neat,cm -1 )2902,2866,2209,1496,1479,1359,1236,1136,1060,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 39 H 41 O5SClNa679.2261,Found 679.2244.

[0183] Example 36

[0184]

[0185] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (171.4 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5w (92.3 mg, 68%) as a colorless liquid. 1 H NMR(400MHz, CDCl3)δ7.40–7.27(m,18H),7.21–7.17(m,2H),5.77(m,1H),5.02–4 .99(m,1H),4.98–4.96(m,1H),4.96–4.91(m,1H),4.90(d,J=8.6Hz,1H),4.83(d, J=10.5Hz,2H),4.62(m,3H),4.35(d,J=8.9Hz,1H),4.24(s,2H),3.79–3.64(m,5H ),3.56–3.51(m,1H),3.48(t,J=6.6Hz,2H),2.11–2.04(m,2H),1.67–1.60(m,2H). 13C NMR (101MHz, CDCl3) δ138.3,138.1,138.0,137.9,128.5,128.4,128.3,128.0,127.8,127.6,114.8,94. 6,86.4,85.4,80.2,80.0,77.6,75.9,75.6,75.2,73.5,72.2,69.3,68.6,59.1,30.3,28.7.IR(neat,cm -1 )3105,2900,2868,2206,1468,1442,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 46 O6SNa701.2913,Found 701.2904.

[0186] Example 37

[0187]

[0188] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (189.5 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was dried and column chromatography yielded 5x (136.0 mg, 92%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.44–7.27(m,18H),7.24–7.19(m,2H),5.03(d,J=10.3Hz,1H),4.93(dd,J=22.1,10.9Hz,2H),4.86(dd,J=10.5,3.9Hz,2H),4. 71(d,J=12.1Hz,1H),4.63(t,J=12.1Hz,2H),4.34(d,J=8.9Hz,1H),3.83– 3.71(m,7H),3.55(m,1H),2.57(t,J=7.1Hz,2H),0.91(s,9H),0.08(s,6H). 13C NMR (101MHz, CDCl3) δ138.6,138.3,138.1,138.0,128.5,128.4,128.3,128.0,127.9,127.8,127.7,127.6,95 .2,86.5,85.5,80.2,80.1,77.7,75.9,75.5,75.2,73.5,68.6,65.5,61.8,25.9,24.7,18.3,-5.2.IR(neat,cm -1 )2906,2868,2210,1498,1479,1359,1236,1134,1058,1039,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 44 H 54 O6SSiNa761.3308,Found 761.3302.

[0189] Example 38

[0190]

[0191] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (172.6 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5y (87.4 mg, 64%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.41–7.29(m,18H),7.23–7.19(m,2H),5.37(s,1H),5.00(d,J=10.3Hz,1H),4.92(q,J=11.0Hz,3H),4.85(d,J=10.6 Hz,3H),4.66(dd,J=19.8,11.5Hz,3H),4.60(d,J=12.2Hz,1H),4.42(d,J=8.9Hz,1H),3.75(m,7H),3.63–3.53(m,3H),1.26–1.19(m,6H). 13C NMR (101MHz, CDCl3) δ138.4,138.2,138.0,137.9,128.5,128.4,128.3,128.0,127.9,127.8,127.6, 92.7,91.9,86.4,85.5,80.4,80.1,77.6,75.8,75.6,75.2,73.5,72.2,68.5,61.1,15.1.IR(neat,cm -1 )2904,2868,2206,1498,1479,1467,1359,1236,1136,1039,1028,738,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 41 H 46 O7SNa 705.2862,Found705.2860.

[0192] Example 39

[0193]

[0194] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (189.5 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5z (125.6 mg, 85%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.40–7.29(m,18H),7.23–7.19(m,2H),5.03(d,J=10.2Hz, 1H), 4.94 (dd, J=23.8, 11.1Hz, 2H), 4.85 (m, 2H), 4.71 (d, J=12.2Hz, 1H), 4.67–4. 62(m,2H),4.54(dd,J=19.7,10.1Hz,1H),4.36(d,J=8.9Hz,1H),3.81–3.70(m,5 H),3.57–3.52(m,1H),1.45(d,J=6.5Hz,3H),0.93(s,9H),0.15(d,J=8.4Hz,6H). 13C NMR (101MHz, CDCl3) δ138.6,138.3,138.1,138.0,128.5,128.4,128.3,128.0,127.9,127.8,127.7,127.6,100.1 ,86.4,85.5,80.3,79.9,77.6,75.7,75.6,75.1,73.5,69.0,68.6,59.9,25.9,25.3,18.3,-4.4,-4.8.IR(neat,cm -1 )2900,2864,2205,1489,1467,1359,1236,1138,1062,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 44 H 54 O6SSiNa 761.3308,Found 761.3298.

[0195] Example 40

[0196]

[0197] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (205.7 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5aa (130.1 mg, 82%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.38–7.25(m,18H),7.17(m,2H),4.99(d,J=10.2Hz,1H),4.85(m,4H),4.59(m,3H),4.36–4.30(m,1H),3 .78–3.61(m,5H),3.50(m,1H),1.79(m,2H),1.62(m,4H),1.56–1.43(m,2H),1.31(m,2H),0.87(s,9H),0.17(m,J=0.5Hz,6H). 13C NMR (101MHz, CDCl3) δ138.5,138.3,138.1,138.0,128.5,128.4,128.3,128.0,127.9,127.8,127.7,102.0,86.6,85 .7,80.4,79.9,77.7,75.8,75.6,75.1,73.7,70.4,70.2,68.9,41.2,26.0,25.3,22.8,18.2,-2.6,-2.7.IR(neat,cm -1 )2906,2882,2206,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 48 H 60 O6SSiNa 815.3778,Found 815.3769.

[0198] Example 41

[0199]

[0200] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (206.3 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5ab (125.6 mg, 79%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.44–7.30(m,18H),7.24–7.20(m,2H),5.01(d,J=10.2Hz,1H),4.95(dd,J=23.0,11.0Hz,2H),4.87(dd,J=10.5,5.9H z,2H),4.64(m,3H),4.42(d,J=9.1Hz,1H),3.88–3.66(m,9H),3.57(m,1H),2.02–1.91(m,2H),1.87–1.75(m,2H),0.94(s,9H),0.24(m,6H). 13C NMR (101MHz, CDCl3) δ138.4,138.1,138.0,137.8,128.5,128.5,128.4,128.3,128.1,128.0,127.9,127.7,100.4,86.5 ,85.6,80.4,79.9,77.6,75.9,75.6,75.2,73.6,71.7,68.8,67.3,64.3,41.2,41.1,25.9,18.2,-2.7,-2.8.IR(neat,cm -1 )2906,2869,2208,1498,1359,1238,1136,1060,1039,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 47 H 58 O7SSiNa817.3570,Found 817.3563.

[0201] Example 42

[0202]

[0203] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (230.9 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5ac (157.9 mg, 90%) as a colorless liquid. 1 H NMR(400MHz, CDCl3)δ7.72(d,J=7.3Hz,4H),7.49–7.34(m,22H),7.33–7.27(m,4H),4.97(m, 4H), 4.79–4.65 (m, 4H), 4.53 (d, J = 9.2Hz, 1H), 3.92–3.58 (m, 6H), 1.10 (s, 9H), 0.18 (m, 6H). 13C NMR (101MHz, CDCl3) δ146.7,138.7,138.2,138.1,138.0,128.6,128.5,128.3,128.2,128.1,128.0,127.8,127.7,127.6,127 .4,126.5,126.4,100.1,86.5,85.9,80.4,79.9,77.6,76.6,76.0,75.6,75.5,75.2,73.7,68.9,26.2,18.6,-3.0.IR(neat,cm -1 )2904,2882,2209,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 55 H 60 O6SSiNa 899.3778,Found899.3764.

[0204] Example 43

[0205]

[0206] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and purified by column chromatography to afford 5ad (70.9 mg, 54%) as a white solid. 1 H NMR (500MHz, CDCl3) δ7.48–7.45(m,2H),7.44–7.41(m,2H),7.41–7.21(m,21H),5.04(m,2H),4.95(d,J=10.2Hz,1H),4.81(q,J=11.7 Hz,2H),4.65(d,J=11.6Hz,1H),4.55(d,J=11.7Hz,1H),4.49(m,2H),4.32(t,J=9.3Hz,1H),4.07(d,J=2.7Hz,1H),3.77–3.68(m,4H). 13C NMR (126MHz, CDCl3) δ138.9,138.2,137.8,131.5,128.5,128.4,128.2,128.1,127.9,127.8,127.7 ,127.5,127.4,123.3,96.8,86.4,83.9,77.9,75.9,75.2,74.7,73.8,73.7,72.7,68.4.IR(neat,cm -1 )2902,2880,2204,1498,1359,1236,1136,1060,1039,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 40 O5SNa 679.2494,Found 679.2482.Mp:67.5–68.2℃.

[0207] Example 44

[0208]

[0209] A carbohydrate compound (84 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5ae (66.6 mg, 62%) as a colorless liquid. 1 H NMR (500MHz, CDCl3) δ7.46(m,4H),7.40–7.30(m,16H),5.04(d,J=10.3Hz,1H),4.91(m,3H),4.75(d,J=11.6Hz,1H),4.66(d,J= 11.6Hz,1H),4.44(d,J=9.0Hz,1H),4.14(dd,J=11.6,4.2Hz,1H),3.81(t,J=8.8Hz,1H),3.76–3.66(m,2H),3.40–3.30(m,1H). 13 C NMR (126MHz, CDCl3) δ138.4,138.0,132.0,128.7,128.6,128.5,128.4,128.3,128.1,128.0, 127.9,127.8,122.9,96.7,86.4,85.2,79.6,77.6,75.8,75.7,74.6,73.4,68.2.IR(neat,cm-1 )2904,2880,2205,1498,1479,1238,1126,1062,1039,1028,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 34 H 33 O4S 537.2100,Found537.2091.

[0210] Example 45

[0211]

[0212] A carbohydrate compound (52 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and reacted at 25°C for 16 hours. After the reaction was complete, the mixture was dried and column chromatography was performed to obtain a colorless liquid 5af (54.2 mg, 72%). βisomer: 1 H NMR (500MHz, CDCl3) δ7.50–7.41(m,2H),7.37–7.28(m,3H),5.27(d,J=2.6Hz,1H),4.43(m,1H),4.12(m,1H),4.00(dd,J=10.9,5.6 Hz,1H),3.94–3.83(m,2H),3.26(m,1H),1.59(s,3H),1.53(s,3H),1.41(m,6H). 13 C NMR (126 MHz, CDCl3) δ131.9,128.3,122.9,110.8,99.8,94.8,85.1,76.5,75.0,72.1,70.0,61.8,29.0,28.1,26.2,18.8.

[0213] αisomer: 1 H NMR(500 MHz, CDCl3)δ7.45–7.41(m,2H),7.29(m,3H),5.14(d,J=3.9Hz,1H),4.89(m,1H),4.82 (m,1H),4.50(m,1H),4.15(m,2H),3.61(m,1H),1.53(s,3H),1.40(s,3H),1.37(m,6H). 13C NMR (126 MHz, CDCl3) δ131.8,128.3,114.0,109.4,91.0,81.7,81.4,80.2,72.9,67.1,27.1,25.7,25.2,25.0.IR(neat,cm -1 )2902,2884,2202,1496,1479,1359,1234,1135,1062,1038,1028,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 25 O5S 377.1423, Found 377.1415.

[0214] Example 46

[0215]

[0216] A carbohydrate compound (69.6 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and reacted at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5ag (49.2 mg, 53%) as a colorless liquid. 1 H NMR (500 MHz, CDCl3) δ7.52–7.48(m,2H),7.35–7.31(m,3H),5.35–5.25(m,2H),5.17–5.11(m,1H),4.62(d,J=9.5 Hz,1H),4.26(m,1H),4.19(m,1H),3.80(m,1H),2.10(s,3H),2.06(s,3H),2.03(s,3H),2.02(s,3H). 13 C NMR (126 MHz, CDCl3) δ170.7,170.2,169.3,169.0,132.1,128.9,128.3,122.6,97.1,84.5,76.5,73.9,72.6,69.8,67.9,62.0,20.7,20.6.

[0217] Example 47

[0218]

[0219] A carbohydrate compound (84 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and reacted at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5ah (73.0 mg, 68%) as a colorless liquid. 1 H NMR (400 MHz, CDCl3) δ7.44–7.39(m,2H),7.39–7.21(m,18H),5.93(d,J=5.5 Hz,1H),4.74(m,2H),4.64(d,J=11.7 Hz,1H),4.53(dd,J=12.0,3.5 Hz,2H),4.47–4.37(m,2H),4.22(t,J=5.6 Hz,1H),3.98(m,1H),3.62(m,1H),3.54(m,1H). 13 C NMR(101 MHz, CDCl3)δ138.0,137.9,137.3,131.6,128.5,128.4,128.2,128.0,127.9,1 27.8,127.7,93.4,81.9,79.5,78.3,76.6,73.6,73.3,72.7,69.0.IR(neat,cm -1 )2904,2882,2206,1496,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 34 H 33 O4S 537.2100,Found 537.2090.

[0220] Example 48

[0221]

[0222] A carbohydrate compound (52 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and reacted at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5ai (48.9 mg, 65%) as a colorless liquid. 1H NMR (500 MHz, CDCl3) δ7.42 (m, 2H), 7.29 (m, 3H), 5.13 (d, J = 3.9 Hz,1H),4.88(m,1H),4.81(m,1H),4.50(m,1H),4.15(m,2H),3.61(dd,J=8.3,3.4Hz,1H),1.53(s,3H),1.45(s,3H),1.37(m,6H). 13 C NMR (126MHz, CDCl3) δ131.8,128.3,114.0,109.4,91.0,81.7,81.4,80.2,72.9,67.1,27.1,25.7,25.2,25.0.IR(neat,cm -1 )2902,2884,2207,1485,1479,1359,1236,1134,1060,1036,1028,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 20 H 25 O5S 377.1423, Found 377.1409.

[0223] Example 49

[0224]

[0225] A carbohydrate compound (205.8 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded a colorless liquid 5aj (108.9 mg, 79%). 11H NMR (400 MHz, CDCl3) δ 7.67 (m, 2H), 7.59–7.50 (m, 6H), 7.43–7.21 (m, 15H), 7.17 (m, 2H), 5.46 (d, J = 3.7 Hz, 1H), 5.36–5.28 (m, 2H), 5.22 (m, 2H), 4.83 (dd, J = 10.3, 3.7 Hz, 1H), 4.56 (d, J = 9.6 Hz, 1H), 4.34 (m, 5H), 4.12 (t, J = 9.3 Hz, 1H), 4.04–3.90 (m, 2H), 3.73 (d, J = 9.1 Hz, 1H), 3.48 (d, J = 10.6 Hz, 2H), 3.27 (dd, J = 11.7, 3.2 Hz, 1H), 2.86 (s, 1H), 2.09 (d, J = 2.5 Hz, 6H), 2.06 (s, 3H), 1.99 (s, 3H), 1.87 (s, 3H), 0.97 (s, 9H), 0.89 (s, 9H). 13 13C NMR (101 MHz, CDCl3) δ 170.5, 170.4, 170.3, 169.4, 169.1, 136.2, 135.7, 135.4, 133.5, 133.0, 132.6, 132.1, 129.7, 129.6, 128.7, 128.2, 127.7, 127.6, 122.8, 113.2, 95.3, 84.1, 80.0, 77.3, 76.4, 73.1, 71.5, 70.8, 70.6, 70.0, 68.0, 62.6, 61.6, 45.0, 29.7, 26.9, 26.7, 21.2, 21.0, 20.7, 20.6, 19.2, 19.1, 9.5. IR (neat, cm -1 ) 2903, 2880, 2201, 1496, 1479, 1347, 1236, 1060, 1039, 1028, 732, 694. HRMS (ESI) m / z: [M+Na] + Calcd for C 62 H 72 O 15 SSi2Na 1167.4028, Found 1167.4031.

[0226] Example 50

[0227]

[0228] A carbohydrate compound (281 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (164.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5ak (240.5 mg, 79%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.46–7.42(m,2H),7.40–7.15(m,51H),7.09(m,2H),5.17(d,J=3. 4Hz,1H),4.95(d,J=11.4Hz,1H),4.93–4.82(m,6H),4.80(d,J=7.6Hz,1H),4.77–4.68(m ,5H),4.59(m,8H),4.51(d,J=11.7Hz,2H),4.46–4.36(m,3H),4.10(m,4H),4.02(s,1H), 3.95(m,3H),3.86(d,J=12.5Hz,2H),3.80(m,2H),3.70–3.57(m,5H),3.54–3.45(m,2H). 13 C NMR (101MHz, CDCl3) δ140.0,138.9,138.8,138.7,138.6,138.3,138.1,137.8,132 .4,128.5,128.4,128.3,128.2,128.1,127.9,127.7,127.4,122.8,98.1,97.3,86 .4,86.1,80.6,80.1,79.4,78.2,77.7,77.3,76.8,75.7,75.6,75.4,75.3,75.1,7 5.0,74.9,74.8,73.7,73.4,72.9,72.8,72.6,69.3,69.1,66.4,65.2.IR(neat,cm -1 )2902,2884,2206,1486,1359,1236,1136,1062,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 96 H 96 O 15 SNa 1543.6368,Found1543.6365.

[0229] Example 51

[0230]

[0231] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (221.3 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5al (145.4 mg, 86%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.39–7.25(m,18H),7.21–7.16(m,2H),5.01(d,J=10.2 Hz,1H),4.93(d,J=11.1Hz,1H),4.90–4.78(m,3H),4.66–4.52(m,3H),4.37(d d,J=6.6,2.6Hz,1H),3.78–3.61(m,5H),3.52(m,1H),2.20(m,4H),1.92(s,2H ),1.78–1.62(m,6H),1.49(dd,J=12.4,2.6Hz,2H),0.92(s,9H),0.20(m,6H). 13 C NMR (101MHz, CDCl3) δ138.5,138.3,138.1,138.0,128.5,128.4,128.3,128.1,128.0,127.9,127.8,127.7,101.9,86.5,85.7,80 .6,79.9,77.6,75.8,75.6,75.1,74.7,73.7,71.9,69.0,40.0,38.0,35.4,35.3,31.9,27.0,26.9,26.2,18.6,-2.6.IR(neat,cm -1 )2904,2880,2203,1498,1482,1358,1234,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 52 H 64 O6SSiNa 867.4091,Found 867.4085.

[0232] Example 52

[0233]

[0234] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (246.5 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5am (113.4 mg, 61%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.41–7.32(m,36H),7.24–7.20(m,4H),7.06(d,J=7.5Hz,2H),6.71(d,J=7.5Hz,2H),6. 65(s,2H),5.07(dd,J=10.2,3.3Hz,2H),5.03–4.97(m,2H),4.94(m,2H),4.87(m,4H),4.74–4.59(m,6H),4.4 0(m,2H),4.27(d,J=11.6Hz,2H),3.95(m,4H),3.88–3.66(m,11H),3.62–3.54(m,2H),2.35(s,6H),2.25(s,6 H),1.88–1.78(m,4H),1.67–1.54(m,4H),0.99(s,10H),0.97(s,9H),0.26(s,3H),0.23(s,3H),0.17(m,6H). 13 C NMR (101MHz, CDCl3) δ157.2,138.6,138.5,138.3,138.2,138.1,138.0,136.4,130.4,128.5,1 28.4,128.3,128.0,127.9,127.8,127.7,123.7,120.7,112.1,98.6,98.0,86.5,85.8,85.5,8 0.6,80.3,79.9,77.7,77.6,75.8,75.6,75.1,73.6,71.9,71.8,70.7,70.6,69.0,68.8,68.6, 39.3,39.3,34.6,34.5,25.9,24.4,23.2,23.1,21.5,18.3,15.9,-3.9,-4.0,-5.1.IR(neat,cm -1 )2902,2880,2202,1497,1478,1359,1236,1136,1060,1039,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 57 H 72O7SSiNa 951.4666,Found951.4643.

[0235] Example 53

[0236]

[0237] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (217.7 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5an (141.6 mg, 85%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.45(d,J=7.2Hz,2H),7.38–7.28(m,16H),7.25–7.16(m,5H),5.11(d,J=1 0.2Hz,1H),5.01–4.83(m,4H),4.74(d,J=12.1Hz,1H),4.64(t,J=12.2Hz,2H),4.43(dd,J=9.3, 2.6Hz,1H),3.89(t,J=8.8Hz,1H),3.83(s,2H),3.81–3.72(m,2H),3.59(m,1H),2.89–2.76(m,2 H),2.38(m,2H),2.24–1.87(m,4H),1.65(m,12H),1.00(d,J=7.2Hz,1H),0.94(d,J=1.4Hz,3H). 13C NMR (101MHz, CDCl3) δ141.5,140.7,138.4,138.1,138.0,136.9,136.7,132.5,129.5,129.3,128.5,128.4,128.0 ,127.9,127.8,127.5,125.4,124.5,124.0,120.3,120.0,119.2,97.0,96.8,86.5,85.6,83.4,80.2,77.6,77.3, 75.9,75.7,75.2,73.9,73.6,68.6,50.5,49.7,48.0,46.7,44.5,44.4,39.3,38.0,36.6,35.9,34.9,34.6,34.4, 31.7,31.6,31.5,30.3,29.8,29.3,29.1,27.3,26.3,26.1,25.9,25.6,23.7,23.5,21.6,14.4,13.9.IR(neat,cm -1 )2904,2882,2204,1498,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 54 H 56 O6SNa855.3695,Found 855.3697.

[0238] Example 54

[0239]

[0240] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (240.5 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography afforded 5ao (92.7 mg, 51%) as a colorless liquid. 11H NMR (400 MHz, CDCl3) δ 7.69–7.58 (m, 5H), 7.40–7.27 (m, 30H), 7.24–7.15 (m, 6H), 7.05 (m, 2H), 6.94 (d, J = 2.5 Hz, 1H), 4.90 (d, J = 11.5 Hz, 2H), 4.85–4.78 (m, 3H), 4.67 (dd, J = 10.4, 4.3 Hz, 2H), 4.64–4.50 (m, 8H), 4.19 (d, J = 8.9 Hz, 1H), 3.86 (s, 2H), 3.81 (s, 3H), 3.73–3.58 (m, 8H), 3.53–3.40 (m, 3H), 3.19–3.07 (m, 2H), 1.45 (m, 6H), 0.88 (s, 9H), 0.81 (s, 6H), 0.03 (s, 5H), -0.05 (s, 3H), -0.11 (s, 2H). 13 13C NMR (101 MHz, CDCl3) δ 157.3, 157.2, 138.6, 138.5, 138.3, 138.2, 138.0, 137.9, 133.5, 129.3, 129.2, 128.9, 128.8, 128.5, 128.4, 128.3, 128.0, 127.9, 127.8, 127.7, 127.6, 127.5, 127.3, 126.8, 126.5, 126.4, 118.6, 105.6, 98.8, 86.4, 85.5, 85.3, 80.3, 80.0, 79.9, 79.6, 77.6, 77.5, 75.7, 75.6, 75.4, 75.3, 75.1, 73.6, 73.5, 70.9, 69.3, 68.8, 55.2, 46.8, 25.9, 25.8, 18.2, 18.1, 16.7, 16.5, -4.5, -5.2, -5.3. IR (neat, cm -1 ) 2908, 2884, 2209, 1498, 1480, 1358, 1234, 1136, 1060, 1039, 1028, 732, 694. HRMS (ESI) m / z: [M+Na] + Calcd for C 56 H 64 O7SSiNa 931.4040, Found 931.4031.

[0241] Example 55

[0242]

[0243] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (325.8 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5ap (138.5 mg, 58%) as a colorless liquid. 1 H NMR(400MHz, CDCl3)δ8.03(dd,J=7.3,2.6Hz,1H),7.98–7.91(m,1H),7.71(m,1H),7.60(d,J=5.3Hz,1H),7.55–7.44(m,26 H),7.40–7.33(m,3H),7.31–7.24(m,3H),5.68(d,J=9.1Hz,1H),5.61(d,J=7.4Hz,2H),5.19–4.95(m,5H),4.81(m,2H),4. 77–4.70(m,1H),4.68–4.60(m,1H),4.50(m,1H),3.97(m,3H),3.92(s,1H),3.89–3.80(m,3H),3.78–3.56(m,2H),3.14–3. 08(m,2H),2.98(s,3H),2.13–2.00(m,2H),1.29–1.21(m,4H),0.94(s,9H),0.11(d,J=5.2Hz,3H),-0.01(d,J=4.3Hz,3H). 13 C NMR (101MHz, CDCl3) δ156.8,154.3,143.4,140.1,139.7,139.6,138.9,138.8,138.6,138.2,138.1,138.0,13 6.3,135.2,135.0,130.2,130.1,129.6,128.5,128.4,128.3,128.1,128.0,127.9,127.6,126.0,123.8,123. 0,122.9,119.0,109.9,109.2,99.4,86.4,85.7,85.6,80.2,79.9,79.8,79.7,77.7,77.6,75.6,75.5,75.1,7 3.5,73.3,72.5,68.7,68.5,62.9,47.0,31.9,29.9,25.7,21.8,18.1,17.0,14.2,-4.5,-4.6,-5.IR(neat,cm -1)2904,2880,2207,1498,1362,1238,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 75 H 81 O6SSiN41193.5646,Found 1193.5647.

[0244] Example 56

[0245]

[0246] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (240.5 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and reacted at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5aq (167.3 mg, 92%) as a white solid. 1 H NMR (500MHz, CDCl3) δ7.37–7.24(m,18H),7.18–7.11(m,2H),5.72(s,1H),5.24(d,J=3.5Hz,1H),5.01 –4.89(m,1H),4.87–4.67(m,4H),4.63–4.45(m,3H),4.07–3.94(m,1H),3.73–3.52(m,4H),2.83–2.73( m,1H),2.41–2.33(m,2H),2.30–2.25(m,1H),2.12(s,3H),1.97(m,1H),1.85–1.76(m,3H),1.66–1.55( m,4H),1.44(dd,J=13.1,3.6Hz,1H),1.34(m,2H),1.18(s,3H),1.04(s,3H),1.01(m,1H),0.88(m,1H). 13C NMR (126MHz, CDCl3) δ208.1,199.4,171.3,170.8,138.7,138.3,138.0,137.9,1 28.5,128.4,128.2,128.1,128.0,127.9,127.8,127.7,127.6,124.0,96.2,91.3 ,81.8,80.1,77.8,75.7,75.0,73.5,73.2,70.2,68.7,53.0,47.0,38.5,35.7,35 .6,33.9,33.6,32.9,32.7,31.5,27.0,24.6,21.1,20.7,17.4,14.9.IR(neat,cm -1 )2906,2882,2206,1746,1498,1479,1359,1236,1136,1060,1039,1028,732,694.HRMS(EI)m / z:[M+Na] + Calcd for C 57 H 64 O8SNa 931.4220,Found 931.4206.Mp:119.6–121.3℃.

[0247] Example 57

[0248]

[0249] A carbohydrate compound (108 mg, 0.2 mmol, 1 equiv), an imidazole alkynyl sulfide reagent (296.4 mg, 0.3 mmol, 1.5 equiv), BTMG (80.6 μl, 0.4 mmol, 2 equiv), and acetone (2 mL) were added to a reaction tube and allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and purified by column chromatography to afford 5ar (122.7 mg, 56%) as a white solid. 11H NMR (500 MHz, CDCl3) δ 7.39–7.27 (m, 18H), 7.15 (dd, J = 7.0, 2.4 Hz, 2H), 5.29 (d, J = 1.4 Hz, 1H), 5.15 (d, J = 3.0 Hz, 1H), 5.02 (d, J = 10.1 Hz, 1H), 4.93 (d, J = 11.3 Hz, 1H), 4.87 (d, J = 11.3 Hz, 1H), 4.83–4.77 (m, 2H), 4.60 (m, 3H), 4.34 (d, J = 9.3 Hz, 1H), 3.83–3.69 (m, 5H), 3.63 (t, J = 9.3 Hz, 1H), 3.54 (m, 1H), 2.30–2.11 (m, 3H), 2.01–1.90 (m, 2H), 1.83–1.59 (m, 10H), 1.43–1.10 (m, 7H), 0.99 (s, 3H), 0.96 (s, 9H), 0.91 (s, 9H), 0.87 (s, 3H), 0.22 (s, 3H), 0.19 (s, 4H), 0.16 (m, 6H). 13 13C NMR (126 MHz, CDCl3) δ 150.4, 141.2, 138.6, 138.2, 138.1, 137.9, 128.5, 128.4, 128.2, 128.0, 127.9, 127.8, 127.6, 127.5, 118.2, 109.1, 101.7, 86.5, 85.5, 81.7, 80.7, 79.8, 77.9, 75.7, 75.3, 73.6, 71.6, 68.9, 50.4, 48.5, 48.2, 40.3, 34.9, 34.1, 33.0, 32.7, 31.6, 27.7, 25.9, 25.7, 23.5, 21.0, 19.1, 18.3, 18.1, 13.3, -2.9, -4.1, -4.4. IR (neat, cm<< -1 ) 2904, 2880, 2208, 1498, 1479, 1358, 1234, 11[]36, 1062, 1039, 732, 694. HRMS (ESI) m / z: [M + H] + Calcd for C 67 [[ID=[]8]]H 91 O7SSi2 1095.6024, Found 1095.6020.

[0250] Example 58

[0251]

[0252] To a reaction tube, add a glucosinolate (65.7 mg, 0.1 mmol, 1 equiv), DIBAL-H (0.1 mL, 0.1 mmol, 1.0 equiv, 1.0 M in n-hexane), n-BuLi (0.04 mL, 0.1 mmol, 1.0 equiv, 2.5 M in n-hexane), and n-hexane (2 mL). Incubate at 0-80°C for 0.5 h. After completion, the reaction was evaporated to dryness and column chromatography afforded 6a (46.7 mg, 71%) as a colorless oil. 1 H NMR(400MHz, CDCl3)δ7.39(d,J=7.5Hz,2H),7.31–7.28(m,2H),7.25–7.17(m,18H),7.16–7.11(m,3 H),6.30(d,J=10.9Hz,1H),6.02(d,J=10.9Hz,1H),4.63(d,J=11.5Hz,1H),4.60(d,J=9.6Hz,1H),4. 56(d,J=3.2Hz,1H),4.49(s,2H),4.45(d,J=9.9Hz,2H),3.93(m,1H),3.86–3.80(m,2H),3.75(dd,J =7.0, 4.0Hz, 1H), 3.56 (d, J = 4.3Hz, 2H), 2.98 (dd, J = 14.0, 5.0Hz, 1H), 2.82 (dd, J = 13.9, 6.2Hz, 1H). 13 C NMR (101MHz, CDCl3) δ138.1,138.0,137.9,137.8,136.9,128.7,128.6,128.5,128.3,128. 0,127.9,127.8,127.6,126.7,125.8,78.9,78.6,74.3,73.5,73.4,71.1,71.0.IR(neat,cm -1 )3108,1688,1486,1479,1358,1236,1136,1060,1039,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 42 O5SNa 681.2651,Found 681.2642.

[0253] Example 59

[0254]

[0255] To a reaction tube, add the glucosinolate (65.7 mg, 0.1 mmol, 1 equiv), DIBAL-H (0.1 mL, 0.1 mmol, 1.0 equiv, 1.0 M in n-hexane), n-BuLi (0.04 mL, 0.1 mmol, 1.0 equiv, 2.5 M in n-hexane), and tetrahydrofuran (2 mL). Incubate at 0-80°C for 0.5 h. After completion, spin-dry the reaction and column chromatography afforded 6b (55.9 mg, 85%) as a white solid. Mp: 75.2–75.9°C. 1 H NMR (500MHz, CDCl3) δ7.38–7.29(m,23H),7.23–7.20(m,2H),6.95(dd,J=15. 7,2.3Hz,1H),6.80(dd,J=15.7,2.1Hz,1H),4.97–4.93(m,2H),4.90(dd,J=1 1.0,2.1Hz,1H),4.87(dd,J=10.7,2.0Hz,1H),4.80(dd,J=10.3,1.9Hz,1H), 4.66–4.61(m,4H),4.60–4.56(m,1H),3.83–3.71(m,5H),3.65–3.57(m,2H). 13 C NMR (126MHz, CDCl3) δ138.5,138.2,138.0,137.9,136.7,131.8,128.7,128.5,128.4,128.0,127.9,127 .8,127.6,127.5,126.0,120.6,86.6,84.9,81.3,79.6,77.8,75.8,75.5,75.2,73.6,68.9.IR(neat,cm -1 )3100,1686,1498,1479,1359,1237,1136,1062,1039,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 42 O5SNa 681.2651,Found 681.2639.

[0256] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0257] As used in the present invention, the term "comprising" is an open expression, that is, including the contents specified in the present invention, but not excluding other aspects.

[0258] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0259] The protection content of the present invention is not limited to the above embodiments. Without departing from the spirit and scope of the inventive concept, changes and advantages that can be thought of by those skilled in the art are included in the present invention and are protected by the appended claims.

Claims

1. An imidazolyl alkynyl sulfide reagent, characterized in that The structure of the imidazole alkynyl sulfide reagent is shown in formula (3): Among them, R 1 Selected from hydrogen, benzene ring, substituted benzene ring, heteroaromatic ring, alkyl, active molecule; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ether-substituted phenyl, amino-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene; the active molecule is selected from adamantane, naproxen, telmisartan, isoxetine, opsazone, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, bezafibrate, estrone.

2. A method for synthesizing an imidazole alkynyl sulfide reagent, characterized in that: The bromoimidazole sulfonate shown in formula (1) is used as a reaction raw material. Under the action of an activation reagent and NaSbF6, it reacts with the alkyne shown in formula (2) in an organic solvent to obtain the imidazole alkynyl sulfide reagent shown in formula (3). The reaction process is shown in reaction formula (a): in, R 1 Selected from hydrogen, benzene ring, substituted benzene ring, heteroaromatic ring, alkyl, active molecule; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ether-substituted phenyl, amino-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene; the active molecule is selected from adamantane, naproxen, telmisartan, isoxetine, opsazone, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, bezafibrate, estrone.

3. The synthesis method according to claim 2, wherein The activation reagent is selected from one or more of zinc bromide, zinc chloride, and n-butyl lithium; and / or the organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, toluene, and n-hexane; and / or the reaction temperature is -78 to 25°C; and / or the reaction time is 1 to 16 hours; and / or the amount ratio of the bromoimidazole sulfonate represented by formula (1), the alkyne represented by formula (2), the activation reagent, NaSbF6, and the organic solvent is 1 mol: (1-3) mol: (2-5) mol: (2-5) mol: (5-10) volume.

4. Use of an imidazole alkynyl thio reagent in the selective construction of glucosidic compounds, characterized in that: The saccharide compound represented by formula (4) and the imidazole alkynyl sulfide reagent represented by formula (3) are used as reaction raw materials. Under the action of a base, in an organic solvent, a glucosidoglycoside compound represented by formula (5) is obtained. The reaction process is shown in reaction formula (b): in, R is selected from benzyl, acyl, alkyl, and silicon; R 1 Selected from hydrogen, benzene ring, substituted benzene ring, heteroaromatic ring, alkyl group, active molecule; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ether-substituted phenyl, amino-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene; the active molecule is selected from adamantane, naproxen, telmisartan, isoxetine, opsazone, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, bezafibrate, estrone; n is selected from an integer of 4-6.

5. The use according to claim 4, characterized in that The base is selected from one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium tert-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide monohydrate, pyridine, 2,6-lutidine, 2,4,6-trimethylpyridine, triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, tetramethylguanidine, and 2-tert-butyl-1,1,3,3-tetramethylguanidine; and / or the organic solvent is selected from one or more of dichloromethane, toluene, tetrahydrofuran, nitromethane, toluene, chloroform, acetone, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, and ethyl acetate.

6. The use according to claim 4, characterized in that The reaction temperature is -78 to 50° C.; and / or the reaction time is 8 to 24 hours; and / or the amount ratio of the saccharide compound, the base, the imidazole alkynyl sulfide reagent and the organic solvent is 1 mol: (1.5 to 3.1) mol: (1.5 to 3) mol: (5 to 10) volume.

7. Use of a glucosinolate compound in constructing a glucosinolate derivative, characterized in that: The glucosidic compound represented by formula (5) is used as the reaction raw material, and under the action of an activation reagent, in an organic solvent, a reaction is carried out to obtain a glucosidic compound derivative represented by formula (6). The reaction process is shown in reaction formula (c): in, R is selected from benzyl, acyl, alkyl, and silicon; R 1 is selected from hydrogen, a benzene ring, a substituted benzene ring, a heteroaromatic ring, an alkyl group, and an active molecule; wherein the substituted benzene ring is selected from a halogen-substituted phenyl group, an alkyl-substituted phenyl group, an ether-substituted phenyl group, an amino-substituted phenyl group, an alkynyl-substituted phenyl group, a trifluoromethyl-substituted phenyl group, a polysubstituted phenyl group, anthracene, and naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, and thiophene; the active molecule is selected from adamantane, naproxen, telmisartan, isoxetine, opsazone, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, bezafibrate, and estrone; R 2 is selected from primary alkyl and substituted olefin; wherein the primary alkyl is selected from α-acetophenone, and the substituted olefin is selected from styrene, borate-substituted styrene, cyano and chlorine-substituted styrene; and n is selected from an integer of 4-6.

8. The use according to claim 7, characterized in that The ratio of the glucosidic compound represented by formula (5), the activating reagent and the organic solvent is 1 mol: (1-3) mol: (5-10) volume; and / or, the organic solvent is selected from one or more of n-hexane, tetrahydrofuran, toluene and 1,2-dichloroethane; and / or, the activating reagent is selected from one or more of DIBAL-H, n-butyl lithium, borate and hydrogen peroxide; and / or, the reaction temperature is 0-80° C.; and / or, the reaction time is 0.5-3 hours.

9. A glucosinolate compound, characterized in that Its structural formula is shown in formula (5): Wherein, R is selected from benzyl, acyl, alkyl, and silicon; R 1 Selected from hydrogen, benzene ring, substituted benzene ring, heteroaromatic ring, alkyl group, active molecule; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ether-substituted phenyl, amino-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene; the active molecule is selected from adamantane, naproxen, telmisartan, isoxetine, opsazone, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, bezafibrate, estrone; n is selected from an integer of 4-6.

10. A glucosinolate derivative, characterized in that: Its structural formula is shown in formula (6): Wherein, R is selected from benzyl, acyl, alkyl, and silicon; R 2 is selected from primary alkyl and substituted olefin; wherein the primary alkyl is selected from α-acetophenone, and the substituted olefin is selected from styrene, borate-substituted styrene, cyano and chlorine-substituted styrene; and n is selected from an integer of 4-6.

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