Tetramethyl aryl thiourea reagent, synthesis method thereof and application of tetramethyl aryl thiourea reagent in selective construction of thioglycoside

Abstract

The invention discloses a tetramethyl aryl thiourea reagent, a synthesis method thereof and application of the tetramethyl aryl thiourea reagent in selective construction of thioglycoside, according to the method, arylamine shown in a formula (1) is used as a reaction raw material, and under the action of an activating reagent and a catalyst, the tetramethyl aryl thiourea reagent shown in a formula (3) is obtained through a reaction in an organic solvent; the thioglycoside compound is obtained by taking sugar as shown in a formula (4) and a tetramethyl aryl thiourea reagent as shown in a formula (3) as reaction raw materials and reacting in an organic solvent under the action of alkali. 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 provided by the invention can be used for constructing a novel tetramethyl aryl thiourea 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 a tetramethylarylthiourea reagent and a synthesis method thereof, and application thereof in the selective construction of glucosinolates. 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 synthesis of glucosinolates, the present invention utilizes tetramethylarylthiourea reagents. This reaction is highly efficient and selective, requiring no pre-functionalization of the reaction substrates or the presence of transition metals. It directly utilizes readily available raw materials to yield diverse, stereospecific glucosinolates. In light of this, the present invention devises a reaction method for preparing tetramethylarylthiourea reagents by reacting aromatic amines with another molecule of tetramethylthiourea. Furthermore, a reaction method for preparing glucosinolates by reacting tetramethylarylthiourea reagents with another molecule of a carbohydrate compound in the presence of a base is also devised.

[0005] The present invention provides a tetramethyl aryl thiourea reagent, the structure of which is shown in formula (3):

[0006]

[0007] in,

[0008] Ar is selected from a benzene ring, a substituted benzene ring, a heteroaromatic ring, a substituted heteroaromatic ring, and an aromatic ring containing an active molecule.

[0009] Preferably, Ar is selected from a benzene ring, a substituted benzene ring, a heteroaromatic ring, a substituted heteroaromatic ring, and an aromatic ring containing an active molecule; wherein the substituted benzene ring is selected from a halogen-substituted phenyl, an alkyl-substituted phenyl, an ester-substituted phenyl, a nitro-substituted phenyl, an alkynyl-substituted phenyl, a trifluoromethyl-substituted phenyl, a polysubstituted phenyl, anthracene, and naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene, thiazole, and pyridazine; the substituted heteroaromatic ring is selected from a halogen-substituted pyridazine and an ester-substituted thiophene; and the active molecule in the aromatic ring containing an active molecule is selected from amino acids, naproxen, telmisartan, podophyllotoxin, isoxacic acid, opsazone, probenecid, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, indomethacin, bezafibrate, and noproxol.

[0010] Further preferably, Ar is selected from a benzene ring, a substituted benzene ring, a heteroaromatic ring, a substituted heteroaromatic ring, and an aromatic ring containing an active molecule; wherein the substituted benzene ring is selected from a fluorine-substituted phenyl, a chlorine-substituted phenyl, a bromine-substituted phenyl, an iodine-substituted phenyl, a methyl-substituted phenyl, an isopropyl-substituted phenyl, a tert-butyl-substituted phenyl, an ethyl formate-substituted phenyl, a nitro-substituted phenyl, an alkynyl-substituted phenyl, a trifluoromethyl-substituted phenyl, a piperonyl-substituted phenyl, a 2,4-dichloro-substituted phenyl, a 2-fluoro Substituted phenyl, 4-chloro substituted phenyl, perfluoro substituted phenyl, anthracene, naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene, thiazole, pyridazine; the substituted heteroaromatic ring is selected from 2,6-dichloro substituted pyridazine, methyl formate substituted thiophene; the active molecule in the aromatic ring containing the active molecule is selected from amino acids, naproxen, telmisartan, podophyllotoxin, isoxacic acid, opsazone, probenecid, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, indomethacin, bezafibrate, novofil.

[0011] The present invention also provides a method for synthesizing a tetramethylarylthiourea reagent, comprising the following steps:

[0012] Step 1: Using the aromatic amine represented by formula (1) as a reaction raw material, reacting in a solvent under the action of an activation reagent and tetrafluoroboric acid to obtain a product;

[0013] Step 2: Add tetramethylthiourea shown in formula (2) to the product obtained in step 1, and react in an organic solvent under the action of a catalyst to obtain a tetramethylarylthiourea reagent shown in formula (3). The reaction process is shown in reaction formula (a):

[0014]

[0015] Wherein, Ar is defined as described in Formula 3.

[0016] In the present invention, in reaction formula (a), the activation reagent is selected from one or more of sodium nitrite, hydrochloric acid, sulfuric acid, etc.; preferably, it is sodium nitrite;

[0017] In the present invention, in reaction formula (a), the catalyst includes one or more of cuprous chloride, cupric chloride, copper iodide, cuprous iodide, etc.; preferably, it is cupric chloride;

[0018] In the present invention, in reaction formula (a), the solvent is selected from one or more of water, acetone, ethanol, methanol, tetrahydrofuran, etc.; preferably, it is one or two of water and acetone;

[0019] In the present invention, in reaction formula (a), the organic solvent is selected from one or more of acetone, ethanol, methanol, tetrahydrofuran, etc.; preferably, it is acetone;

[0020] In the present invention, in reaction formula (a), the ratio of the activation reagent, tetrafluoroboric acid, the catalyst, the solvent, the organic solvent, the tetramethylthiourea and the aromatic amine is (1-2) mol: (1-2) mol: (0.1-1) mol: (5-10) volume: (5-10) volume: 1 mol: (1-2) mol; preferably, 1 mol: 1 mol: 0.1 mol: 10 volume: 10 volume: 1 mol: 1 mol;

[0021] In the present invention, in reaction formula (a), the temperature of the first and second steps of the reaction is 0 to 25°C; preferably, 25°C;

[0022] In the present invention, in reaction formula (a), the reaction time of the first step and the second step is 1-16 hours; preferably, 2 hours;

[0023] In the present invention, in reaction formula (a), the reaction is carried out in an air atmosphere.

[0024] The present invention also provides a tetramethyl aryl thiourea reagent compound of formula (3) obtained by the above method. Further, the tetramethyl aryl thiourea reagent compound of formula (3) of the present invention includes the following and Table 1:

[0025]

[0026] The present invention also proposes an application of a tetramethylarylthiourea reagent in the selective construction of a glucosidic compound, wherein a sugar represented by formula (4) and a tetramethylarylthiourea reagent represented by formula (3) are used as reaction raw materials, and a glucosidic compound represented by formula (5) is obtained by reaction in an organic solvent under the action of a base. The reaction process is shown in reaction formula (b):

[0027]

[0028] wherein n is selected from an integer of 1-100; R 2is selected from alkyl, acyl, and silicon; Ar is as defined in Formula 3;

[0029] Preferably, n is selected from an integer of 1-10; R 2 Selected from alkyl groups containing aromatic groups, alkyl acyl groups, and bulky hindered silicon groups;

[0030] More preferably, n is selected from an integer between 4 and 6; R 2 Selected from benzyl.

[0031] 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 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG);

[0032] 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 chloroform;

[0033] In the present invention, in reaction formula (b), the ratio of the sugar, the base, the organic solvent and the tetramethylarylthiourea reagent is 1 mol: (1.5-3.1) mol: (5-10) volume: (1.5-3) mol; preferably, 1 mol: 3.1 mol: 10 volume: 3 mol;

[0034] In the present invention, in reaction formula (b), the reaction temperature is -78 to 50°C; preferably, 25°C;

[0035] In the present invention, in reaction formula (b), the reaction time is 8-24 hours; preferably, 16 hours;

[0036] In the present invention, in reaction formula (b), the reaction is carried out in an air atmosphere.

[0037] The present invention also provides a glucosidoglycoside compound, the structure of which is shown in formula (5):

[0038]

[0039] in,

[0040] n is an integer selected from 1 to 100; n, R 2The definition of is the same as described in reaction formula (b); the definition of Ar is the same as described in formula 3.

[0041] Furthermore, the glucosinolate compounds are shown in Table 2.

[0042] The present invention also proposes an application of a glucosinolate compound in the construction of an oxidized glucosinolate compound, wherein the glucosinolate represented by formula (5) is used as a reaction raw material, and under the action of an oxidant, in an organic solvent, a reaction is performed to obtain an oxidized glucosinolate compound represented by formula (6). The reaction process is shown in reaction formula (c):

[0043]

[0044] in,

[0045] n、R 2 The definition of is the same as described in reaction formula (b); the definition of Ar is the same as described in formula 3.

[0046] In the present invention, in reaction formula (c), the organic solvent is selected from one or more of chloroform, dichloromethane, methanol, ethanol, etc.; preferably, it is chloroform;

[0047] In the present invention, in reaction formula (c), the oxidant is selected from one or more of m-chloroperbenzoic acid, hydrogen peroxide, etc.; preferably, it is m-chloroperbenzoic acid;

[0048] In the present invention, in reaction formula (c), the ratio of the glucosinolate represented by formula (5) to the organic solvent and the oxidant is 1 mol: (5-10) volume: (2-3) mol; preferably, 1 mol: 10 volume: 2.5 mol;

[0049] In the present invention, in reaction formula (c), the reaction temperature is 25 to 70°C; preferably, 25°C;

[0050] In the present invention, in reaction formula (c), the reaction time is 8-16 hours; preferably, it is 8 hours.

[0051] The present invention also provides an oxidized glucosinolate compound, the structure of which is shown in formula (6):

[0052]

[0053] Among them, n, R 2 The definition of is the same as described in reaction formula (b); the definition of Ar is the same as described in formula 3.

[0054] Furthermore, the oxidized sulfosuccinate compounds are shown in Table 3.

[0055] In a specific embodiment, the synthesis reaction of the present invention is carried out in a reaction flask A, and an aromatic amine (1 mmol) represented by formula (1), tetrafluoroboric acid (1 mmol), sodium nitrite (1 mmol), and a solvent (10 mL) are added to the reaction flask A, and the reaction system is stirred at 0° C. in an air atmosphere for 10 minutes; after the reaction is completed, an organic solvent (10 mL), tetramethylthiourea (1 mmol) represented by formula (2), and cuprous chloride (0.1 mmol) are added to the reaction flask A, and the reaction system is stirred 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., a tetramethylarylthiourea reagent represented by formula (3), is obtained by column chromatography.

[0056] In another specific embodiment, the synthesis reaction of the present invention is carried out in a reaction flask B, and a sugar (0.2 mmol) represented by formula (4), a tetramethylarylthiourea reagent (0.6 mmol) represented by formula (3), a base (0.62 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 8 hours; after the reaction is completed, silica gel is added and dried, and the target product, i.e., a glucosidoglycoside compound represented by formula (5), is obtained by column chromatography.

[0057] 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 oxidant (0.22 mmol), and an organic solvent (1 mL) are added to the reaction flask C, and the reaction system is stirred at 25° C. under an air atmosphere for 8 hours; after the reaction is completed, silica gel is added and dried, and the target product, i.e., an oxidized glucosinolate compound represented by formula (6), is obtained by column chromatography.

[0058] The present invention also provides a tetramethylarylthiourea reagent compound as shown in formula (3) prepared according to the above-mentioned synthesis method of the present invention.

[0059] The present invention also proposes that the tetramethylarylthiourea reagent compound represented by formula (3) can be used as or for preparing glucosinolates.

[0060] The present invention also proposes that the glucosinolate compound represented by formula (5) can be used as or for preparing oxidized glucosinolates.

[0061] The yields of the tetramethylarylthiourea reagent compound represented by formula (3) and the glucosidoglycoside compound represented by formula (5) prepared by the synthesis method of the present invention are 55% or more.

[0062] 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 tetramethylarylthiourea reagent is simple to prepare, stable, and has no irritating odor; and the reaction conditions are relatively mild. The tetramethylarylthiourea reagent of the present invention reacts with a carbohydrate compound to produce a glucosidic compound. The reaction operation is simple, the reaction conditions are relatively mild, and the compound can be used to construct a novel glucosidic compound, making it suitable for large-scale industrial production. DETAILED DESCRIPTION

[0063] 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.

[0064] 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.

[0065] 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.

[0066] The present invention discloses a method for synthesizing a tetramethylarylthiourea reagent and its application in selectively constructing glucosinolates. The method uses an aromatic amine represented by formula (1) as a reaction raw material, reacts in an organic solvent under the action of an activating reagent and a catalyst to obtain the tetramethylarylthiourea reagent represented by formula (3); and uses a sugar represented by formula (4) and the tetramethylarylthiourea reagent represented by formula (3) as reaction raw materials, reacts in an organic solvent under the action of a base to obtain the glucosinolate compound. 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 tetramethylarylthiourea reagents and glucosinolate compounds, and has broad application prospects and practical value.

[0067] 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.

[0068] The synthesis reaction of the tetramethylarylthiourea reagent and the sulfosuccinate compound of the present invention comprises the following steps:

[0069] As shown in reaction formula (a), the synthesis reaction of the present invention is to add the aromatic amine shown in formula (1), an activating reagent, and a solvent to a reaction flask A, and stir the reaction system at 0°C in an air atmosphere for 10 minutes; after the reaction is completed, an organic solvent, a catalyst, and tetramethylthiourea shown in formula (2) are added, and the reaction system is stirred 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 tetramethyl aryl thiourea reagent shown in formula (3), is obtained by column chromatography. The novel tetramethyl aryl thiourea reagent of the present invention is shown in Table 1.

[0070] As shown in reaction formula (b), the synthesis reaction of the present invention is carried out in a reaction flask B, wherein the saccharide compound represented by formula (4), the tetramethylarylthiourea reagent represented by formula (3), a base, and an organic solvent are added. The reaction system is stirred at 25°C under air for 8 hours. After the reaction is completed, silica gel is added and dried by spin drying. The target product, i.e., the glucosinolate compound represented by formula (5), is obtained by column chromatography. The novel glucosinolate compounds of the present invention are shown in Table 2.

[0071] As shown in reaction formula (c), the synthesis reaction of the present invention is carried out by adding a glucosinolate compound represented by formula (5), an oxidant, and a solvent to a reaction flask C, and stirring the reaction system at 25°C under air for 8 hours. After the reaction is completed, silica gel is added and dried by spin drying, and the target product, i.e., an oxidized glucosinolate compound represented by formula (6), is obtained by column chromatography. The novel oxidized glucosinolate compounds of the present invention are shown in Table 3.

[0072] The tetramethylarylthiourea reagents shown in Table 1 are all products synthesized by the method of the present invention. There is no public document that discloses these compounds.

[0073] Table 1 New tetramethylarylthiourea reagent of the present invention

[0074]

[0075]

[0076]

[0077] 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.

[0078] Table 2 New glucosido compounds of the present invention

[0079]

[0080]

[0081]

[0082]

[0083] The oxidized glucosinolate compounds shown in Table 3 are all products synthesized by the method of the present invention, and no public literature has disclosed these compounds.

[0084] Table 3 New oxidized glucosinolate compounds of the present invention

[0085]

[0086] Example 1

[0087]

[0088] To a reaction tube, an aromatic amine (931 mg, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3a (2.19 g, 74%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.43 (s, 5H), 3.19 (s, 12H). 13 C NMR (101MHz, CDCl3) δ174.41,131.69,130.67,130.05,127.79,44.05. 19 F NMR(376MHz,CDCl3)δ-152.76.IR(neat,cm -1 )2930,1650,1582,1236,1156,1028,996,796,742,693.HRMS(ESI)m / z:[M]+Calcd for C 11 H 17 SN2209.1107,Found 209.1096.Mp:80.5-81.3℃.

[0089] Example 2

[0090]

[0091] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 min. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and column chromatography afforded 3b (2.45 g, 79%) as a yellow viscous substance. 1 H NMR (400MHz, CDCl3) δ7.33 (d, J = 7.6Hz, 2H), 7.25 (d, J = 7.2Hz, 2H), 3.23 (s, 12H), 2.34 (s, 3H). 13 C NMR (101MHz, CDCl3) δ174.90,140.70,132.16,131.47,124.17,44.41,21.32. 19 F NMR(376MHz, CDCl3)δ-152.75,-152.80.IR(neat,cm -1 )2932,1652,1568,1147,1028,821,742,693.HRMS(ESI)m / z:[M]+Calcd for C 12 H 19 SN2223.1263,Found 223.1258.

[0092] Example 3

[0093]

[0094] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and column chromatography afforded 3c (2.91 g, 86%) as a yellow viscous substance. 1 H NMR (400MHz, CDCl3) δ7.35 (d, J = 8.0Hz, 2H), 7.28 (d, J = 7.9Hz, 2H), 3.20 (s, 12H), 2.88 (m, 1H), 1.20 (d, J = 6.9Hz, 6H). 13CNMR (101MHz, CDCl3) δ174.82,151.42,131.86,128.83,124.35,44.05,33.85,23.69. 19 F NMR(376MHz, CDCl3)δ-152.74,-152.79.IR(neat,cm -1 )2928,1652,1426,1201,1113,856,736,693.HRMS(ESI)m / z:[M]+Calcd for C 14 H 23 SN2251.1576,Found251.1582.

[0095] Example 4

[0096]

[0097] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the mixture was evaporated to dryness and column chromatography afforded 3d (2.50 g, 71%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.44(d,J=8.2Hz,2H),7.35(d,J=8.2Hz,2H),3.20(s,12H),1.26(s,9H). 13 C NMR (101MHz, CDCl3) δ174.73,153.70,131.51,127.72,124.16,44.04,34.89,31.09. 19 F NMR(376MHz, CDCl3)δ-152.78,-152.83.IR(neat,cm -1 )2930,1665,1482,1156,895,744,692.HRMS(ESI)m / z:[M]+Calcd for C 15 H 25 SN2265.1783,Found 265.1759.Mp:96.8-98.1℃.

[0098] Example 5

[0099]

[0100] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 min. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3e (2.14 g, 68%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.54(s,2H),7.19(s,2H),3.29(s,12H). 13 C NMR (101MHz, CDCl3) δ174.44,135.05,134.97,123.10,118.34,118.12,44.78. 19 F NMR(376MHz, CDCl3)δ-108.86,-152.40,-152.46,-152.52.IR(neat,cm -1 )2928,1664,1479,1128,997,732,692.HRMS(ESI)m / z:[M]+Calcd forC 11 H 16 SFN2227.1013,Found227.1009.Mp:123.3-124.5℃.

[0101] Example 6

[0102]

[0103] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 min. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3f (2.15 g, 65%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.43 (m, 4H), 3.21 (s, 12H). 13C NMR (101MHz, CDCl3) δ173.80,136.50,133.18,130.89,126.27,44.17. 19 FNMR(376MHz,CDCl3)δ-152.45,-152.50.IR(neat,cm -1 )2927,1658,1481,1128,984,732,692.HRMS(ESI)m / z:[M]+Calcd for C 11 H 16 SClN2243.0723,Found 243.0726.Mp:106.7-108.2℃.

[0104] Example 7

[0105]

[0106] To a reaction tube, add an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After the reaction is complete, spin-drying is performed and column chromatography is performed to yield 3 g (2.59 g, 69%) of a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.52 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 3.16 (s, 12H). 13 C NMR (101MHz, CDCl3) δ173.55,133.76,133.24,126.97,124.56,44.08. 19 F NMR(376MHz, CDCl3)δ-152.39,-152.44.IR(neat,cm -1 )2929,1558,1325,1156,885,732,692.HRMS(ESI)m / z:[M]+Calcd for C 11 H 16 SBrN2287.0212,Found287.0219.Mp:93.4-94.5℃.

[0107] Example 8

[0108]

[0109] To a reaction tube, add an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After the reaction is complete, spin-drying is performed and column chromatography is performed to obtain 3h (3.04 g, 72%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.58(s,2H),7.07(s,2H),3.21(s,12H). 13 C NMR (101MHz, CDCl3) δ173.79,140.26,134.47,128.02,99.99,96.74,45.63. 19 F NMR(376MHz, CDCl3)δ-152.25,-152.31.IR(neat,cm -1 )2932,1566,1320,1156,885,732,692.HRMS(ESI)m / z:[M]+Calcd for C 11 H 16 SIN2335.0073,Found335.0081.Mp:97.2-98.3℃.

[0110] Example 9

[0111]

[0112] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the mixture was spin-dried and column chromatography afforded 3i (2.83 g, 83%) as a yellow solid. 1 H NMR (400MHz, DMSO-d6) δ8.36 (d, J = 7.5Hz, 2H), 7.86 (d, J = 7.5Hz, 2H), 3.22 (s, 12H). 13C NMR (101MHz, DMSO-d6) δ171.32,148.00,137.55,132.23,125.45,44.27. 19 F NMR(376MHz,DMSO)δ-148.17,-148.30.IR(neat,cm -1 )2932,1670,1584,1309,1125,885,732,692.HRMS(ESI)m / z:[M]+Calcd forC 11 H 16 SO2N3254.0958,Found254.0946.Mp:202.7-203.3℃.

[0113] Example 10

[0114]

[0115] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After the reaction was complete, the product was evaporated to dryness and purified by column chromatography to afford 3j (2.73 g, 75%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.70 (m, 4H), 3.30 (s, 12H). 13 C NMR (101MHz, CDCl3) δ172.93,132.11,127.59,127.56,44.65. 19 F NMR(376MHz, CDCl3)δ-62.93,-152.33,-152.39.IR(neat,cm -1 )2919,1551,1285,1108,901,732,692.HRMS(ESI)m / z:[M]+Calcd for C 12 H 16 SF3N2277.0981,Found 277.0980.Mp:89.3-90.2℃.

[0116] Example 11

[0117]

[0118] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the mixture was spin-dried and column chromatography afforded 3k (3.16 g, 86%) as a white solid. 1 H NMR (400MHz, CDCl3) δ8.07(d,J=8.2Hz,2H),7.55(d,J=8.2Hz,2H),4.34(q,J=7.1Hz,2H),3.23(s,12H),1.36(t,J=7.1Hz,3H). 13 C NMR (101MHz, CDCl3) δ173.18,165.30,133.35,131.65,131.45,131.15,61.60,44.19,14.26. 19 F NMR(376MHz, CDCl3)δ-152.45,-152.51.IR(neat,cm -1 )2919,2390,1548,1278,1156,901,732,692.HRMS(ESI)m / z:[M]+Calcd for C 14 H 21 SO2N2281.1318,Found281.1312.Mp:108.7-110.3℃.

[0119] Example 12

[0120]

[0121] To a reaction tube, an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3l (3.01 g, 89%) as a yellow solid. 1H NMR (400MHz, CDCl3) δ8.01 (d, J = 7.9 Hz, 2H), 7.58 (d, J = 8.0 Hz, 2H), 3.25 (s, 12H), 2.58 (s, 3H). 13 C NMR (101MHz, CDCl3) δ197.02,173.06,137.62,133.57,131.42,130.27,44.31,26.78. 19 F NMR(376MHz, CDCl3)δ-152.30,-152.36.IR(neat,cm -1 )2932,2386,1289,1142,893,732,692.HRMS(ESI)m / z:[M]+Calcd for C 13 H 19 SON2251.1213,Found251.1201.Mp:123.5-124.8℃.

[0122] Example 13

[0123]

[0124] To a reaction tube, add an aromatic amine (1.07 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After the reaction is complete, spin-drying is performed and column chromatography is performed to obtain 3m (2.20 g, 65%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.25 (d, J = 8.7Hz, 2H), 6.66 (d, J = 8.7Hz, 2H), 3.16 (s, 12H), 2.96 (s, 6H). 13 C NMR (101MHz, CDCl3) δ176.61,151.23,133.92,113.31,110.54,43.86,43.69,40.05,38.60. 19 FNMR(376MHz,CDCl3)δ-153.26.IR(neat,cm -1 )2928,1516,1289,1142,893,732,692.HRMS(ESI)m / z:[M]+Calcd for C 13 H 22SN3252.1529,Found 252.1527.Mp:85.8-86.7℃.

[0125] Example 14

[0126]

[0127] To a reaction tube, add an aromatic amine (1.61 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is performed and column chromatography is performed to afford 3n (2.58 g, 71%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.78(d,J=7.8Hz,1H),7.72(t,J=7.6Hz,1H),7.66(d,J=7.8Hz,1H),7.58(t,J=7.5Hz,1H),3.24(s,12H). 13 C NMR (101MHz, CDCl3) δ172.92,134.58,134.46,130.26,127.85,126.78,44.14. 19 FNMR(376MHz, CDCl3)δ-60.47,-152.45,-152.50.IR(neat,cm -1 )2936,1522,1265,1139,901,732,692.HRMS(ESI)m / z:[M]+Calcd for C 12 H 16 SF3N2277.0981,Found 277.0992.Mp:114.7-116.3℃.

[0128] Example 15

[0129]

[0130] To a reaction tube, an aromatic amine (1.69 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the mixture was spin-dried and column chromatography afforded 3o (2.79 g, 75%) as a yellow viscous product. 1 H NMR (400MHz, CDCl3) δ7.59 (d, J = 7.3 Hz, 1H), 7.47 (m, 6H), 7.28 (d, J = 7.1 Hz, 2H), 3.03 (s, 12H). 13 C NMR (101MHz, CDCl3) δ174.29,144.58,138.95,133.50,131.40,130.64,129.83,128.93,128.82,128.76,126.47,43.82. 19 F NMR(376MHz, CDCl3)δ-152.74,-152.79.IR(neat,cm -1 )2927,1543,1263,1128,956,743,694.HRMS(ESI)m / z:[M]+Calcd for C 17 H 21 SN2285.1420,Found 285.1409.

[0131] Example 16

[0132]

[0133] To a reaction tube, add an aromatic amine (1.69 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is performed and column chromatography is performed to obtain 3p (2.94 g, 92%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.54–7.41(m,4H),3.23(s,12H). 13C NMR (101MHz, CDCl3) δ173.71,134.38,133.56,132.02,130.95,128.33,124.60,81.51,80.02,44.16. 19 F NMR(376MHz, CDCl3)δ-152.51,-152.56.IR(neat,cm -1 )3209,2932,1548,1256,1108,848,743,694.HRMS(ESI)m / z:[M]+Calcd forC 13 H 17 SN2233.1107,Found 233.1105.Mp:145.9-146.3℃.

[0134] Example 17

[0135]

[0136] To a reaction tube, add an aromatic amine (1.69 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is performed and column chromatography is performed to afford 3q (2.26 g, 58%) as a yellow viscous product. 1 H NMR (501MHz, DMSO) δ10.02 (s, 1H), 7.48 (d, J = 7.5Hz, 1H), 7.32–7.22 (m, 3H), 3.15 (s, 12H), 3.05 (s, 3H). 13 C NMR(126MHz,DMSO)δ172.66,140.39,131.73,129.75,126.68,122.10,121.32,44.20.IR(neat,cm -1 )2910,1556,1228,1108,901,743,694.HRMS(ESI)m / z:[M]+Calcd forC 12 H 20 S2O2N3302.0991,Found 302.0983.

[0137] Example 18

[0138]

[0139] To a reaction tube, an aromatic amine (1.69 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 min. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3r (2.75 g, 81%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.02 (d, J = 7.0Hz, 1H), 6.98–6.86 (m, 2H), 6.06 (s, 2H), 3.28 (s, 12H). 13 C NMR (101MHz, CDCl3) δ175.05,149.92,149.46,127.40,118.77,112.33,110.24,102.37,44.46. 19 F NMR(376MHz, CDCl3)δ-152.63,-152.68.IR(neat,cm -1 )2926,1580,1236,1110,864,743,694.HRMS(ESI)m / z:[M]+Calcd for C 12 H 17 SO2N2253.1005,Found253.1002.Mp:143.7-145.2℃.

[0140] Example 19

[0141]

[0142] To a reaction tube, add an aromatic amine (1.50 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is performed and column chromatography is performed to afford 3s (1.84 g, 53%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ9.17 (s, 1H), 8.23 ​​(s, 1H), 8.13 (d, J = 7.7Hz, 1H), 7.57 (d, J = 8.0Hz, 1H), 3.26 (s, 12H).13 C NMR (101MHz, CDCl3) δ174.16,128.39,126.63,125.54,124.72,44.26. 19 F NMR(376MHz, CDCl3)δ-152.20,-152.25.IR(neat,cm -1 )2926,1580,1236,1110,864,743,694.HRMS(ESI)m / z:[M]+Calcd for C 12 H 17 SO2N2253.1005,Found 253.1002.Mp:162.9-164.1℃.

[0143] Example 20

[0144]

[0145] To a reaction tube, an aromatic amine (1.62 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3t (1.97 g, 54%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.65 (d, J = 7.7Hz, 1H), 7.52 (s, 1H), 7.41 (d, J = 7.2Hz, 1H), 3.25 (s, 12H). 13 C NMR (101MHz, CDCl3) δ173.22,137.67,136.66,135.78,130.85,129.70,125.55,44.25. 19 F NMR(376MHz, CDCl3)δ-152.43,-152.48.IR(neat,cm -1 )2918,1712,1564,1216,1108,778,742,693.HRMS(ESI)m / z:[M]+Calcd for C 11 H 15 SCl2N2277.0328,Found277.0319.Mp:102.4-103.8℃.

[0146] Example 21

[0147]

[0148] To a reaction tube, add an aromatic amine (2.08 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is performed and column chromatography is performed to obtain 3u (2.18 g, 53%) as a yellow viscous product. 1 H NMR (400MHz, CDCl3) δ7.39–7.22(m,2H),3.28(s,12H). 13 C NMR (101MHz, CDCl3) δ172.14,162.28,159.74,126.50,120.89,117.29,117.04,104.09,44.26. 19 F NMR(376MHz, CDCl3)δ-104.50,-152.08,-152.14.IR(neat,cm -1 )2917,1711,1565,1209,1112,778,742,693.HRMS(ESI)m / z:[M]+Calcd forC 11 H 14 SBrF2N2323.0024,Found 323.0021.

[0149] Example 22

[0150]

[0151] To a reaction tube, add an aromatic amine (1.83 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is performed and column chromatography is performed to obtain 3v (2.01 g, 52%) as a yellow solid. 1 H NMR(400MHz,DMSO-d6)δ3.21(s,12H). 13C NMR (101MHz, DMSO) δ170.27,147.59,145.01,144.37,141.84,139.56,137.04,103.49,103.45,43.87. 19 F NMR(376MHz, DMSO-d6)δ-134.69,-134.75,-148.84,-148.90,-159.16,-159.19,-159.24,-159.25,-159.30,-159.31,-159.33.IR(neat,cm -1 )1711,1632,1566,1223,742,693.HRMS(ESI)m / z:[M]+Calcd for C 11 H 12 SF5N2299.0636,Found 299.0633.Mp:135.2-136.1℃.

[0152] Example 23

[0153]

[0154] To a reaction tube, add an aromatic amine (1.43 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, add acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv). After complete reaction, spin-drying and column chromatography yield 3w (1.76 g, 51%) as a yellow viscous product. 1 H NMR (400MHz, CDCl3) δ8.03(d,J=8.5Hz,1H),7.92(dd,J=17.7,8.2Hz,2H),7.74(d,J=7.2Hz,1H),7.68(t,J=7.7Hz,1H),7.54(m,2H),3.16(s,12H). 13 C NMR (101MHz, CDCl3) δ175.08,134.19,132.76,132.02,131.46,129.31,128.81,127.47,126.51,124.55,123.11,44.00. 19 F NMR(376MHz, CDCl3)δ-152.61,-152.66.IR(neat,cm -1)1733,1645,1602,1249,1110,742,693.HRMS(ESI)m / z:[M]+Calcd for C 15 H 19 SN2259.1263,Found259.1248.

[0155] Example 24

[0156]

[0157] To a reaction tube, add an aromatic amine (1.43 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, add acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv). After complete reaction, spin-dry and column chromatography yield 3x (1.87 g, 54%) as a yellow viscous product. 1 H NMR (400MHz, DMSO-d6) δ8.35(s,1H),8.17(d,J=8.6Hz,1H),8.14–8.02(m,2H),7.73(dd,J=6.0,3.2Hz,2H),7.62(d,J=8.6Hz,1H),3.25(s,12H). 13 C NMR (101MHz, DMSO-d6) δ173.19,133.71,133.00,131.85,130.64,128.39,128.30,128.24,128.03,127.98,126.04,44.19. 19 FNMR(376MHz,DMSO-d6)δ-148.20,-148.25.IR(neat,cm -1 )1732,1639,1602,1249,1110,742,693.HRMS(ESI)m / z:[M]+Calcd for C 15 H 19 SN2259.1263,Found259.1251.

[0158] Example 25

[0159]

[0160] To a reaction tube, an aromatic amine (2.19 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the mixture was spin-dried and column chromatography afforded 3y (2.02 g, 48%) as a yellow solid. 1 H NMR (501MHz, DMSO) δ8.51(d,J=7.7Hz,2H),8.47(t,J=9.2Hz,2H),8.42(d,J=8.9 Hz, 1H), 8.35 (dd, J=14.9, 9.1Hz, 2H), 8.26 (dd, J=7.8, 6.3Hz, 2H), 3.17 (s, 12H). 13 C NMR (126MHz, DMSO) δ174.11,132.56,131.43,131.13,131.00,130.70,130.59,129.7 3,127.68,127.60,127.28,127.08,126.57,124.84,123.64,122.58,121.94,44.10. 19 F NMR(376MHz, CDCl3)δ-152.47,-152.52.IR(neat,cm -1 )1732,1639,1602,1546,1256,1249,1110,742,693.HRMS(ESI)m / z:[M]+Calcdfor C 21 H 21 SN2333.1420,Found 333.1419.Mp:238.4-239.1℃.

[0161] Example 26

[0162]

[0163] To a reaction tube, an aromatic amine (2.23 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3z (2.90 g, 68%) as a yellow solid. 1 H NMR (501MHz, DMSO) δ8.37(d,J=7.6Hz,1H),8.34–8.28(m,2H),8.09–8.05(m,2H),8.03(d,J=7.8Hz,1H),7.78(d,J=8.0Hz,1H),3.30(s,12H). 13 C NMR (126MHz, DMSO) δ183.80,182.14,172.20,135.70,135.48,135.35,135. 25,133.58,133.36,132.81,131.38,127.69,127.48,127.17,44.29,43.30. 19 FNMR(376MHz,CDCl3)δ-152.65,-152.70.IR(neat,cm -1 )2360,1748,1641,1532,1256,1249,1108,742,693.HRMS(ESI)m / z:[M]+Calcd for C 19 H 19 SO2N2339.1167,Found 339.1158.Mp:219.8-220.1℃.

[0164] Example 27

[0165]

[0166] To a reaction tube, add an aromatic amine (1.44 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is completed and column chromatography is performed to afford 3aa (2.01 g, 58%) as a yellow viscous product. 1H NMR (400MHz, CDCl3) δ8.98(s,1H),8.39(d,J=8.3Hz,1H),8.26–8.11(m,2H),7.70(d,J=8.6Hz,1H),7.51(dd,J=8.1,3.8Hz,1H),3.46(s,13H). 13 C NMR (101MHz, CDCl3) δ174.10,136.94,132.49,130.87,125.59,50.81,44.34. 19 F NMR(376MHz, CDCl3)δ-152.11,-152.16.IR(neat,cm -1 )1742,1659,1508,1246,1203,1028,742,693.HRMS(ESI)m / z:[M]+Calcd for C 14 H 18 SN3260.1216,Found260.1209.

[0167] Example 28

[0168]

[0169] To a reaction tube, add an aromatic amine (1.45 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is completed and column chromatography is performed to afford 3ab (1.81 g, 52%) as a yellow viscous product. 1 H NMR (400MHz, DMSO-d6) δ9.04(s,2H),8.42(s,1H),8.22(d,J=8.7Hz,1H),7.92(d,J=8.6Hz,1H),3.23(s,12H). 13 C NMR (101MHz, DMSO-d6) δ201.69,174.30,147.49,142.77,142.36,132.41,132.22,131.69,131.33,43.59,34.77,29.09. 19 F NMR(376MHz,DMSO-d6)δ-148.30,-148.36.IR(neat,cm -1)1662,1548,1256,1209,1028,742,693.HRMS(ESI)m / z:[M]+Calcd for C 13 H 17 SN4261.1168,Found 261.1156.

[0170] Example 29

[0171]

[0172] To a reaction tube, an aromatic amine (941 mg, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3ac (2.52 g, 85%) as a yellow solid. 1 H NMR (501MHz, DMSO) δ8.85(s,1H),8.79(s,1H),8.18(s,1H),7.67(s,1H),3.27(s,12H). 13 C NMR(126MHz,DMSO)δ172.44,151.90,150.77,139.94,126.85,125.57,44.24.IR(neat,cm -1 )1662,1548,1156,1028,742,693.HRMS(ESI)m / z:[M]+Calcd for C 10 H 16 SN3210.1059,Found 210.1058.Mp:88.6-89.8℃.

[0173] Example 30

[0174]

[0175] To a reaction tube, an aromatic amine (1.64 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3ad (2.53 g, 69%) as a yellow solid. 1 H NMR (501MHz, DMSO) δ8.69 (s, 1H), 3.22 (s, 12H). 13 C NMR(126MHz,DMSO)δ169.65,167.66,163.12,149.64,145.07,44.25.IR(neat,cm -1 )1658,1549,1152,1028,742,693.HRMS(ESI)m / z:[M]+Calcd forC9H 13 SCl2N4279.0232,Found279.0233.Mp:198.5-199.8℃.

[0176] Example 31

[0177]

[0178] To a reaction tube, an aromatic amine (1.57 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 min. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3ae (2.59 g, 72%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.73 (d, J = 5.3Hz, 1H), 7.22 (d, J = 5.2Hz, 1H), 3.85 (s, 3H), 3.20 (s, 12H). 13 C NMR (101MHz, CDCl3) δ173.52,161.31,133.52,131.44,129.66,52.87,43.91. 19 F NMR(376MHz, CDCl3)δ-152.81,-152.87.IR(neat,cm-1 )2360,1703,1549,1356,1154,1028,742,693.HRMS(ESI)m / z:[M]+Calcd for C 11 H 17 S2O2N2273.0726,Found 273.0728.Mp:58.2-59.7℃.

[0179] Example 32

[0180]

[0181] To a reaction tube, an aromatic amine (1.57 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 min. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After complete reaction, the product was evaporated to dryness and purified by column chromatography to afford 3af (1.79 g, 59%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.84 (d, J = 3.0Hz, 1H), 7.65 (d, J = 3.1Hz, 1H), 3.27 (s, 12H). 13 C NMR (101MHz, CDCl3) δ171.19,152.78,144.63,125.28,44.34. 19 F NMR(376MHz, CDCl3)δ-152.30,-152.36.IR(neat,cm -1 )1752,1509,1358,1156,1028,758,693.HRMS(ESI)m / z:[M]+Calcd for C8H 14 S2N3216.0624,Found216.0639.Mp:89.3-90.5℃.

[0182] Example 33

[0183]

[0184] To a reaction tube, add an aromatic amine (1.32 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is completed and column chromatography is performed to afford 3ag (3.45 g, 92%) as a yellow viscous product. 1 H NMR (400MHz, DMSO-d6) δ11.82(s,1H),7.84(d,J=2.6Hz,1H),7.38(d,J=8.1Hz,1H) ,7.28(d,J=7.9Hz,1H),7.08(d,J=7.8Hz,1H),7.03(d,J=7.4Hz,1H),2.99(s,12H). 13 C NMR(101MHz,DMSO-d6)δ175.33,136.74,133.09,127.46,123.31,121.58,117.79,113.26,95.07,44.12.IR(neat,cm -1 )3309,1728,1549,1302,1146,1028,758,693.HRMS(ESI)m / z:[M]+Calcd forC 13 H 18 SN3248.1216,Found248.1209.

[0185] Example 34

[0186]

[0187] To a reaction tube, an aromatic amine (3.17 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) were added and reacted at 0°C for 10 minutes. After the reaction was complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) were added. After the reaction was complete, the product was evaporated to dryness and purified by column chromatography to afford 3at (3.95 g, 76%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.44 (d, J = 30.7Hz, 4H), 7.09 (d, J = 26.2Hz, 4H), 6.70 (s, 1H), 3.22 (s, 12H), 2.34 (s, 3H).13 C NMR (101MHz, CDCl3) δ173.68,145.30,140.47,139.86,132.50,129.71,128.66,127.98,127.25,125.59,106.06,44.22,21.31. 19 F NMR(376MHz, CDCl3)δ-62.27,-152.32,-152.52.IR(neat,cm -1 )1726,1560,1342,1132,1028,732,693.HRMS(ESI)m / z:[M]+Calcdfor C 22 H 24 SF3N4433.1668,Found 433.1661.Mp:128.3-129.7℃.

[0188] Example 35

[0189]

[0190] To a reaction tube, add an aromatic amine (2.67 g, 10 mmol, 1 equiv), sodium nitrite (690 mg, 10 mmol, 1 equiv), tetrafluoroboric acid (2 mL, 10 mmol, 1 equiv), and water (5 mL) and react at 0°C for 10 minutes. After the reaction is complete, acetone (50 mL), tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), and copper chloride (134.5 mg, 1 mmol, 0.1 equiv) are added. After complete reaction, spin-drying is performed and column chromatography is performed to obtain 3aw (2.87 g, 61%) as a yellow solid. 1 H NMR (400MHz, DMSO-d6) δ7.73 (s, 1H), 7.37 (d, J = 8.4Hz, 1H), 7.21 (s, 1H), 6.90 (d ,J=7.3Hz,1H),6.86–6.66(m,5H),6.27–6.08(m,3H),2.96(s,3H),2.35(s,12H). 13 C NMR(101MHz,DMSO-d6)δ179.99,176.30,164.48,161.02,140.40,137.92,135.29,134.82,1 33.80,132.58,132.47,129.32,129.05,128.74,126.10,118.99,60.42,49.08.IR(neat,cm -1)3326,1720,1548,1356,1178,1028,732,693.HRMS(ESI)m / z:[M]+Calcd for C 21 H 23 SO3N2383.1424,Found 383.1409.Mp:204.3-205.1℃.

[0191] Example 36

[0192]

[0193] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (177.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5a (125.3 mg, 99%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.59–7.52(m,2H),7.36(m,2H),7.33–7.12(m,21H),4.89–4.77(m ,4H),4.67(dd,J=22.4,10.0Hz,2H),4.53(dd,J=26.6,11.2Hz,3H),3.78–3.43(m,6H). 13 C NMR (101MHz, CDCl3) δ137.4,137.3,137.0,132.8,130.9,127.9,127.4,127.3,126.9,126.8,126.7,126. 6,126.5,126.4,86.4,85.7,79.8,78.1,76.8,76.4,76.1,75.7,74.8,74.4,74.0,72.4,68.0.IR(neat,cm -1 )3028,2902,2870,2360,1496,1481,1452,1355,1134,1056,1028,958,750,731,683.Mp:68.2–70.5℃.

[0194] Example 37

[0195]

[0196] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (186.1 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5b (126.8 mg, 98%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.47(d,J=8.1Hz,2H),7.37(m,2H),7.33–7.21(m,16H),7.16(m,2H),6.99(d,J=8.0Hz,2 H),4.84(m,4H),4.70(d,J=10.4Hz,1H),4.62–4.47(m,4H),3.80–3.55(m,4H),3.52–3.40(m,2H),2.26(s,3H). 13 C NMR (101MHz, CDCl3) δ138.6,138.5,138.3,138.2,137.8,132.8,129.8,128.5,128.4,128.3,128.0 ,127.9,127.8,127.6,87.8,86.9,81.0,79.2,78.0,75.9,75.5,75.1,73.5,69.2,21.2.IR(neat,cm -1 )3030,2904,2864,1496,1454,1359,1132,1056,1028,991,906,808,734,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 41 H 42 O5SNa 669.2651,Found669.2631.Mp:56.7–57.9℃.

[0197] Example 38

[0198]

[0199] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (211.3 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 afforded 5c (82.7 mg, 60%) as a colorless liquid. 1H NMR (400MHz, CDCl3) δ7.51 (d, J = 8.5Hz, 2H), 7.45–7.17 (m, 22H), 4.86 (m, 4H), 4.71 (d,J=10.4Hz,1H),4.65–4.38(m,4H),3.84–3.60(m,4H),3.49(m,2H),1.27(s,9H). 13 C NMR (101MHz, CDCl3) δ150.8,138.5,138.2,132.1,128.5,128.4,128.3,128.0,127.9,127.8,127.7,12 7.6,126.2,126.0,87.6,86.9,80.9,79.2,77.9,75.9,75.4,75.1,73.5,69.2,34.6,31.3.IR(neat,cm -1 )2960,2902,2866,1496,1454,1359,1274,1209,1064,1028,748,732,683,547.

[0200] Example 39

[0201]

[0202] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (188.5 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5d (95.0 mg, 73%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.51–7.42(m,2H),7.33–7.14(m,18H),7.13–7.04(m,2H),6.79(t,J =8.7Hz,2H),4.84–4.61(m,5H),4.52–4.42(m,4H),3.68–3.50(m,4H),3.42–3.31(m,2H). 13 C NMR (101MHz, CDCl3) δ163.9,161.5,138.5,138.3,138.1,134.9,134.8,128.5,128.2,128.0, 127.9,127.7,116.1,115.9,93.6,87.7,86.8,80.9,79.1,77.9,75.9,75.5,75.1,73.5,69.1. 19F NMR(376MHz,CDCl3)δ-113.66(s).IR(neat,cm -1 )2866,2360,1489,1454,1359,1274,1209,1056,1028,831,732,683.Mp:84.2–85.7℃.

[0203] Example 40

[0204]

[0205] To a reaction tube, sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (218.5 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL) were added 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 5e (117.7 mg, 84%) as a white solid. 1 H NMR(400MHz, CDCl3)δ7.61(d,J=8.1Hz,2H),7.38(d,J=8.3Hz,2H),7.36–7.23(m,16H),7.22–7.1 6(m,2H),4.91–4.80(m,4H),4.73(d,J=9.6Hz,2H),4.55(m,3H),3.82–3.60(m,4H),3.53(m,2H). 13 C NMR (101MHz, CDCl3) δ139.5,138.4,138.2,138.0,137.9,130.6,128.5,128.2,128.0,1 27.9,127.8,125.8,125.7,86.7,86.6,80.9,79.2,77.8,75.9,75.6,75.2,73.6,69.1. 19 FNMR(376MHz,CDCl3)δ-62.46(s).IR(neat,cm -1 )2866,2360,1558,1541,1508,1454,1328,1112,1062,1028,748,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 41 H 39 F3O5SNa 723.2368,Found723.2351.Mp:123.3–124.9℃.

[0206] Example 41

[0207]

[0208] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (220.9 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5f (56.4 mg, 40%) as a white solid. 1 H NMR(400MHz, CDCl3) δ7.88(d,J=8.5Hz,2H),7.57(d,J=8.5Hz,2H),7.39–7.10(m,20H),4. 95–4.67(m,5H),4.61–4.47(m,2H),4.35(m,2H),3.82–3.46(m,5H),1.37(t,J=7.1Hz,3H). 13 C NMR (101MHz, CDCl3) δ166.2,140.8,138.4,138.2,138.0,137.9,130.0,129.8,128.5,128.4,128.2,12 8.0,127.8,127.7,86.7,86.5,80.8,79.2,77.8,75.9,75.6,75.1,73.5,69.0,61.0,14.4.IR(neat,cm -1 )2866,1707,1593,1456,1396,1209,1184,1105,1058,1014,993,850,750,732,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 43 H 44 O7SNa 727.2705,Found 727.2690.Mp:79.8–82.0℃.

[0209] Example 42

[0210]

[0211] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (202.9 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the mixture was spin-dried and purified by column chromatography to yield 5 g (133.6 mg, 99%) of a white solid. 1H NMR (400MHz, CDCl3) δ7.79(d,J=8.0Hz,2H),7.62(d,J=8.2Hz,2H),7.35(dt,J=10.4,6.2Hz,18H) ,7.25(m,2H),4.99–4.72(m,6H),4.69–4.50(m,3H),3.87–3.66(m,4H),3.60(m,2H),2.56(s,3H). 13 CNMR(101MHz, CDCl3)δ197.3,141.3,138.3,138.2,138.0,137.8,135.3,129.8,129.1,128.8,128.5,128.4,128.2 ,128.0,127.9,127.8,127.7,126.2,86.7,86.3,80.8,79.2,77.8,75.9,75.6,75.2,73.5,69.1,26.6.IR(neat,cm -1 )2906,1676,1589,1454,1398,1355,1267,1093,1062,1028,821,750,683.Mp:105.3–106.9℃.

[0212] Example 43

[0213]

[0214] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (203.5 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After the reaction is complete, spin dry the product and column chromatography yields 5h (74.3 mg, 55%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.47(d,J=8.9Hz,2H),7.45–7.41(m,2H),7.37–7.23(m,16H),7.19(m,2H),6.53(d,J=8.7Hz ,2H),4.94(d,J=10.3Hz,1H),4.90–4.71(m,4H),4.55(m,4H),3.82–3.57(m,4H),3.48–3.39(m,2H),2.89(s,6H). 13C NMR (101MHz, CDCl3) δ150.5,138.6,138.4,138.2,128.5,128.4,128.3,128.0,127.9,127.8,12 7.7,127.5,112.6,88.2,86.9,80.8,79.1,78.0,75.8,75.3,75.1,73.5,69.3,40.4.IR(neat,cm -1 )2904,2866,1595,1506,1454,1354,1134,1064,1028,810,734,683.HRMS(ESI)m / z:[M+H] + Calcd for C 42 H 46 NO5S 676.3097,Found 676.3071.Mp:91.2–92.5℃.

[0215] Example 44

[0216]

[0217] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (218.5 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction is dried and purified by column chromatography to afford 5i (123.3 mg, 88%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.91–7.82(m,1H),7.60(dd,J=7.5,1.7Hz,1H),7.36(dd,J=7.8,1.4Hz,2H),7.32–7.21(m,18H),7.20 –7.16(m,2H),4.98–4.89(m,2H),4.83(dd,J=10.9,7.4Hz,2H),4.72(dd,J=9.9,5.4Hz,2H),4.54(m,3H),3.79–3.48(m,6H). 13 C NMR (101MHz, CDCl3) δ138.5,138.3,138.1,137.7,134.9,132.6,132.3,128.7,128.6,128. 5,128.1,128.0,127.8,127.7,126.8,87.8,86.9,81.3,79.1,77.9,75.9,75.2,73.6,69.3. 19F NMR(376MHz,CDCl3)δ-60.17(s).IR(neat,cm -1 )2868,1508,1456,1317,1174,1114,1097,1058,1028,997,765,748,736,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 41 H 39 F3O5SNa 723.2368,Found 723.2356.Mp:90.7–92.1℃.

[0218] Example 45

[0219]

[0220] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (223.3 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 was performed to obtain a yellow liquid 5j (138.9 mg, 98%). 1 H NMR(400MHz, CDCl3)δ7.97(d,J=7.2Hz,1H),7.55–7.27(m,26H),7.17(m,2H),5.01(d, J=11.0Hz,1H),4.94(m,2H),4.77–4.63(m,6H),3.96–3.71(m,4H),3.69–3.56(m,2H). 13 C NMR (101MHz, CDCl3) δ141.7,139.7,137.4,137.2,137.0,136.6,133.1,129.1,128.6,127.4,127.3, 127.2,126.9,126.7,125.5,86.7,85.6,80.0,77.9,76.8,74.7,74.4,74.0,72.4,68.2.IR(neat,cm -1 )2866,1496,1463,1454,1359,1274,1259,1062,1026,1008,798,738,732,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 46 H 44 O5SNa 731.2807,Found 731.2789.

[0221] Example 46

[0222]

[0223] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (314.6 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction was spin-dried and column chromatography afforded 5k (151.6 mg, 88%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.66–7.58(m,4H),7.43(d,J=8.3Hz,1H),7.35(m,1H),7.25(d,J=7.3Hz,3H),7.22–7.09(m,11H),7.03(m,7H),6. 82–6.69(m,3H),4.79–4.58(m,5H),4.43(m,4H),4.00–3.88(m,1H),3.74(s,3H),3.66–3.46(m,5H),3.35(m,2H),1.56(d,J=7.2Hz,3H). 13 C NMR (101MHz, CDCl3) δ173.0,157.9,150.6,150.5,138.6,138.3,138.2,138.1, 135.1,134.0,133.5,130.9,129.6,129.5,129.1,128.6,128.5,128.3,128.1,1 28.0,127.9,127.8,127.6,126.3,126.2,122.3,122.1,119.3,105.8,87.7,86. 8,80.9,79.1,77.9,75.9,75.5,75.2,73.5,69.1,55.4,45.7,18.6.IR(neat,cm -1 )1751,1489,1454,1274,1261,1201,1139,1126,1066,1055,1028,763,748,696.HRMS(ESI)m / z:[M+Na] + Calcd for C 54 H 52 O8SNa 883.3281,Found883.3266.Mp:93.2–94.5℃.

[0224] Example 47

[0225]

[0226] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (485.2 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 51 (171.8 mg, 75%) as a yellow solid. 1 H NMR(400MHz, CDCl3)δ7.88(d,J=7.6Hz,1H),7.73–7.61(m,1H),7.42–7.37(m,3H),7 .27(d,J=20.5Hz,5H),7.21–7.02(m,25H),6.94(d,J=7.9Hz,2H),6.66(d,J=8.6Hz,2 H),5.21(s,2H),4.80–4.58(m,5H),4.42(m,4H),3.64–3.50(m,4H),3.45(s,3H),3. 40–3.28(m,2H),2.76–2.69(m,2H),2.64(s,3H),1.68(m,2H),0.86(t,J=7.3Hz,3H). 13 C NMR (101MHz, CDCl3) δ166.2,156.5,154.6,150.3,143.3,142.6,141.0,138.5,138.3,138.1,1 36.7,135.2,135.0,133.3,132.7,132.3,131.2,130.7,129.6,129.5,129.3,128.6,128.5,128 .3,128.1,127.9,127.8,126.2,124.0,122.7,122.5,121.9,119.5,109.8,109.0,87.7,86.7, 81.0,79.0,77.8,75.9,75.5,75.2,73.4,69.0,47.1,31.8,29.9,21.9,17.1,14.2.IR(neat,cm -1 )1741,1487,1452,1274,1197,1062,1037,1028,906,746,732,692.HRMS(ESI)m / z:[M+H] + Calcd for C 73 H 69O7SN41145.4887,Found 1145.4882.Mp:82.5–84.1℃.

[0227] Example 48

[0228]

[0229] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (441.9 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, spin-dry the mixture and column chromatography yielded 5m (212.5 mg, 99%) as a yellow liquid. 1 H NMR(400MHz, CDCl3)δ7.81(d,J=8.5Hz,2H),7.52(d,J=8.5Hz,2H),7.27–7.14(m,18H),7.12–7.07(m,2H),6.75 (s,1H),6.47(s,1H),6.33(s,2H),5.98–5.93(m,1H),5.83(dd,J=4.8,1.0Hz,3H),4.78(d,J=4.5Hz,1H),4.75– 4.68(m,3H),4.64(d,J=10.4Hz,1H),4.49(d,J=3.4Hz,2H),4.44(dd,J=22.4,8.2Hz,2H),4.34–4.27(m,1H),4. 17(t,J=9.7Hz,1H),3.67(s,3H),3.65(s,3H),3.61(s,3H),3.59–3.53(m,2H),3.51–3.41(m,2H),2.84(m,2H). 13 C NMR (101MHz, CDCl3) δ173.7,166.4,152.7,148.2,147.8,142.3,138.3,138.1 ,137.9,137.8,137.1,134.9,132.5,130.1,129.7,128.5,128.4,128.2,128.0 ,127.8,127.6,109.8,108.1,107.2,101.7,86.6,86.2,80.7,79.2,77.5,75.9 ,75.6,75.2,74.3,73.4,71.5,68.9,60.7,56.1,45.5,43.8,38.9.IR(neat,cm -1)2868,2360,1772,1714,1645,1635,1589,1483,1456,1375,1363,1274,1261, 1124,1103,1066,1035,997,975,954,856,763,729,696.HRMS(ESI)m / z:[M+Na] + Calcd for C 63 H 60 O 14 SNa1095.3601,Found 1095.3601.

[0230] Example 49

[0231]

[0232] Sugar (194.6 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (282.3 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 was performed to obtain 5n (225.5 mg, 91%) as a white solid. βisomer: 1 H NMR (400MHz, CDCl3) δ8.12(d,J=8.4Hz,1H),7.75(s,1H),7.60(d,J=1.4Hz,1H),7.49–7.41(m,3H),7.37–7. 15(m,31H),7.11(d,J=7.4Hz,2H),6.95(d,J=8.7Hz,2H),5.10(d,J=10.5Hz,1H),4.96(d,J=11.4Hz,1H),4.8 2(t,J=10.7Hz,4H),4.76–4.65(m,4H),4.57–4.48(m,2H),4.40(dd,J=17.5,9.8Hz,2H),4.28(dd,J=40.7,1 1.8Hz,2H),3.99(t,J=9.4Hz,1H),3.91(d,J=2.6Hz,1H),3.84–3.75(m,6H),3.66(m,1H),3.55–3.32(m,6H). 13C NMR(101MHz,CDCl3)δ176.0,159.7,156.1,152.3,142.4,139.1,138.9,138.8,138.5,138.3,138.2,138.0,130.2,128.5,128.4,128.3,128.2,128.1,127.9,127.8,127.6,127.5,127.3,126.6,126.5,125.1,124.1,122.8,118.2,114.1,103.0,86.1,84.9,82.6,80.1,79.6,76.5,75.7,75.7,75.5,74.8,73.7,73.5,73.3,73.2,72.7,68.5,68.2,55.4.IR(neat,cm -1 )2923,2864,1495,1454,1366,1239,1187,1070,1028,908,748,732,694.HRMS(ESI)m / z:[M+H] + Calcdfor C 77 H 75 O 13 S1239.4928,Found 1239.4926.

[0233] αisomer: 1 H NMR(400MHz,CDCl3)δ8.15(d,J=8.4Hz,1H),7.87(s,1H),7.57(d,J=1.6Hz,1H),7.49(d,J=8.8Hz,2H),7.41(dd,J=8.5,1.7Hz,1H),7.38–7.11(m,34H),6.96(d,J=8.8Hz,2H),5.77(d,J=5.5Hz,1H),4.99(dd,J=19.2,11.1Hz,2H),4.83–4.65(m,8H),4.51(m,2H),4.39–4.22(m,5H),4.12(m,1H),3.96(m,1H),3.91–3.89(m,1H),3.86(m,1H),3.81(s,3H),3.77(dd,J=18.3,9.0Hz,3H),3.58–3.45(m,3H),3.41–3.30(m,4H). 13CNMR (101MHz, CDCl3) δ176.1,159.7,156.3,152.3,143.3,139.1,138.8,138.6,138.2,138 .0,137.8,130.2,128.5,128.4,128.3,128.2,128.1,128.0,127.9,127.8,127.7,127.6,1 27.5,127.3,126.4,126.1,122.5,117.4,114.1,103.0,85.8,82.6,80.6,80.0,78.6,76.4 ,75.6,75.4,74.8,73.7,73.5,73.3,73.2,73.1,72.6,71.9,68.3,68.1,55.4.IR(neat,cm -1 )2922,2866,1456,1424,1157,1070,1028,908,748,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 77 H 75 O 13 S1239.4928,Found 1239.4927.Mp:81.8–83.2℃.

[0234] Example 50

[0235]

[0236] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (202.9 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 5o (83.7 mg, 62%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.51(d,J=8.2Hz,2H),7.44–7.23(m,18H),7.18m,2H),7.06(d,J=8.2Hz,2H),4.86(m,4H),4. 72(d,J=10.3Hz,1H),4.65–4.51(m,4H),3.83–3.58(m,4H),3.54–3.43(m,2H),2.84(m,1H),1.21(d,J=6.9Hz,6H). 13C NMR (101MHz, CDCl3) δ148.5,138.5,138.4,138.2,132.5,130.3,128.5,128.4,128.3,128.0,127.9,127.8 ,127.7,127.3,127.1,87.7,86.8,80.9,79.1,77.9,75.9,75.4,75.1,73.5,69.2,33.8,23.9.IR(neat,cm -1 )2956,2899,2868,1496,1452,1398,1355,1340,1141,1083,1055,1028,829,748,727,683,555.HRMS(ESI)m / z:[M+Na] + Calcd for C 43 H 46 O5SNa 697.2964,Found 697.2941.Mp:51.4–52.8℃.

[0237] Example 51

[0238]

[0239] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (198.4 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was spin-dried and column chromatography afforded 5p (124.1 mg, 93%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.51–7.45(m,2H),7.38–7.23(m,18H),7.17(m,2H),7.13(d,J=8.5Hz, 2H),4.91–4.77(m,4H),4.72(d,J=10.3Hz,1H),4.56(m,4H),3.79–3.57(m,4H),3.46(m,2H). 13 C NMR (101MHz, CDCl3) δ138.4,138.3,138.1,138.0,133.8,133.5,132.2,129.1,128.5,128.2, 128.0,127.9,127.8,87.3,86.8,80.9,79.1,77.9,75.9,75.5,75.1,73.5,69.1.IR(neat,cm -1)2866,1558,1541,1508,1473,1456,1134,1091,1062,750,683.Mp:107.2–108.4℃.

[0240] Example 52

[0241]

[0242] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (225.0 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5q (138.1 mg, 97%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.42 (d, J = 8.0Hz, 2H), 7.39–7.22 (m, 20H), 7.21–7.12 (m, 2H), 4. 95–4.78(m,4H),4.77–4.65(m,1H),4.65–4.44(m,4H),3.91–3.59(m,5H),3.48(m,1H). 13 C NMR (101MHz, CDCl3) δ138.5,138.3,138.1,138.0,133.6,132.1,128.6,128.5,128.3,128.1, 127.9,127.8,121.9,87.2,86.8,80.9,79.1,77.9,75.9,75.5,75.2,73.5,69.1.IR(neat,cm -1 )2906,2868,1496,1473,1452,1355,1284,1213,1132,1085,1062,1028,989,817,746,732,692.Mp:92.4–93.6℃.

[0243] Example 53

[0244]

[0245] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (204.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was spin-dried and column chromatography afforded 5r (131.5 mg, 97%) as an orange solid.1 H NMR(400MHz, CDCl3)δ7.95(d,J=8.9Hz,2H),7.56(d,J=8.9Hz,2H),7.36–7.22(m,18H), 7.18(m,2H),5.77(d,J=5.2Hz,1H),4.93–4.66(m,6H),4.53(m,3H),3.85–3.41(m,6H). 13 C NMR (101MHz, CDCl3) δ146.3,144.4,138.3,138.0,137.9,137.7,129.5,128.6,128.5,128.2, 128.0,127.8,124.0,86.7,85.9,80.8,79.3,77.8,75.9,75.7,75.2,73.6,69.1.IR(neat,cm -1 )2866,2360,1508,1496,1454,1338,1274,1209,1056,1028,831,738,683.Mp:95.2–96.7℃.

[0246] Example 54

[0247]

[0248] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (192.1 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction is dried and purified by column chromatography to afford 5s as a white solid (130.0 mg, 99%). 1 H NMR (400MHz, CDCl3) δ7.70(t,J=1.5Hz,1H),7.58–7.50(m,1H),7.39–7.21(m,18H),7.19–7.10(m,4H),4.84(m,4H),4.72(d,J=1 0.4Hz,1H),4.65(d,J=9.8Hz,1H),4.58(t,J=10.9Hz,2H),4.51(d,J=12.1Hz,1H),3.69(m,4H),3.54–3.44(m,2H),2.98(s,1H). 13C NMR (101MHz, CDCl3) δ138.5,138.4,138.2,138.1,135.2,134.5,132.3,131.2,128.9,128.6,128.5,128.3,128.0,1 27.9,127.8,127.7,123.0,87.3,86.8,83.1,81.0,79.3,78.0,77.9,77.4,75.9,75.6,75.1,73.6,69.0.IR(neat,cm -1 )2902,2868,1558,1456,1120,1082,1053,1028,987,752,732,682.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 40 O5SNa 679.2494,Found 679.2471.Mp:78.8–79.9℃.

[0249] Example 55

[0250]

[0251] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (204.0 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was evaporated to dryness and column chromatography afforded 5t (94.8 mg, 70%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.42–7.36(m,2H),7.35–7.20(m,16H),7.19–7.15(m,2H),7.13(d,J=1.7Hz,1H),7.07(dd,J=8 .0,1.8Hz,1H),6.64(d,J=8.0Hz,1H),5.86(s,2H),4.92–4.70(m,5H),4.54(m,4H),3.78–3.58(m,4H),3.44(m,2H). 13C NMR (101MHz, CDCl3) δ148.0,147.9,138.5,138.4,138.2,128.5,128.4,128.3,128.0,127.9,127.8,127.6, 127.5,125.1,114.1,108.6,101.4,88.1,86.9,80.9,79.2,77.9,75.9,75.4,75.1,73.5,69.1.IR(neat,cm -1 )2902,2866,1496,1479,1467,1359,1236,1136,1060,1039,1028,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 41 H 40 O7SNa699.2392,Found 699.2374.Mp:71.4–72.1℃.

[0252] Example 56

[0253]

[0254] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (211.9 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction is dried and purified by column chromatography to afford 5u (103.5 mg, 75%) as a white solid. 1 H NMR (400MHz, CDCl3) δ9.00(s,1H),8.43(d,J=1.4Hz,1H),7.79(d,J=8.4Hz,1H),7.73(dd,J=8.4,1.6Hz,1H),7.49–7.42(m ,2H),7.41–7.29(m,16H),7.25–7.20(m,2H),5.02–4.75(m,6H),4.71–4.54(m,3H),3.89–3.68(m,4H),3.64–3.52(m,2H). 13C NMR (101MHz, CDCl3) δ154.8,153.7,138.5,138.3,138.1,138.0,133.2,132.0,129.7,128.5,128.4,128.3,128.0 ,127.9,127.8,127.6,127.1,122.1,87.7,86.8,81.0,79.2,77.8,77.4,75.9,75.6,75.1,73.6,69.0.IR(neat,cm -1 )2866,1489,1456,1132,1095,1062,1028,827,746,734,683.HRMS(ESI)m / z:[M+H] + Calcd for C 41 H 40 NO5S2690.2348,Found 690.2325.Mp:79.8–80.5℃.

[0255] Example 57

[0256]

[0257] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (219.0 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5v (127.7 mg, 91%) as a white solid. 1 H NMR(400MHz, CDCl3)δ7.60(d,J=8.6Hz,1H),7.41–7.34(m,3H),7.34–7.24(m,16H), 7.19(m,2H),6.96(dd,J=8.6,2.2Hz,1H),4.87(m,4H),4.73(t,J=9.8Hz,2H),4.54(m 3H),3.63(m,6H). 13 C NMR (101MHz, CDCl3) δ138.4,138.2,138.0,137.7,134.8,133.0,132.1,129.4,128.5,128.1, 128.0,127.9,127.8,86.7,86.1,81.0,79.2,77.8,75.9,75.8,75.2,73.6,69.1.IR(neat,cm -1)2866,2360,1558,1541,1508,1450,1361,1132,1068,1056,1029,987,750,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 40 H 38 Cl2O5SNa 723.1715,Found 723.1693.Mp:112.9–113.7℃.

[0258] Example 58

[0259]

[0260] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (246.6 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5w (103.2 mg, 69%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.42(m,2H),7.39–7.24(m,18H),7.19(m,2H),7.11(d,J=6.2Hz,2H),5.01(d,J=10.3 Hz,1H),4.86(m,4H),4.71(d,J=8.9Hz,1H),4.61(d,J=10.9Hz,1H),4.55–4.39(m,2H),3.81–3.35(m,6H). 13 C NMR (101MHz, CDCl3) δ138.4,138.3,138.0,137.9,128.5,128.4,128.3,128.0,127.8,1 27.6,115.9,115.7,115.6,86.6,85.7,82.2,79.6,77.8,75.8,75.6,75.1,73.5,68.9. 19 FNMR(376MHz,CDCl3)δ-101.37(s).IR(neat,cm -1 )2866,2360,1734,1558,1454,1409,1357,1274,1064,1018,856,839,731,683,576.HRMS(ESI)m / z:[M+Na] + Calcd for C 40 H 37BrF2O5SNa 769.1411,Found 769.1405.Mp:52.1–52.8℃.

[0261] Example 59

[0262]

[0263] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (231.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction is dried and purified by column chromatography to yield 5x (101.2 mg, 70%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.40–7.14(m,20H),4.93(d,J=10.4Hz,1H),4.89–4.75(m,4H),4.61(dd,J =33.1,10.2Hz,2H),4.46(q,J=12.1Hz,2H),3.72–3.56(m,4H),3.56–3.47(m,1H),3.36(m,1H). 13 C NMR (101MHz, CDCl3) δ138.3,138.1,138.0,137.7,128.5,128.4,128.2,128.1,128.0,1 27.9,127.8,127.7,127.5,86.6,85.6,82.1,79.6,77.6,75.9,75.7,75.1,73.5,68.7. 19 FNMR(376MHz, CDCl3)δ-130.40–-130.48(m,2F),-151.03–-151.15(m,1F),-160.87–-160.97(m,2F).IR(neat,cm -1 )2902,2868,1485,1456,1353,1134,1083,1066,1028,975,862,746,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 40 H 35 F5O5SNa 745.2023,Found 745.2000.Mp:122.1–123.4℃.

[0264] Example 60

[0265]

[0266] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (207.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 5y (97.0 mg, 71%) as a brown solid. 1 H NMR (400MHz, CDCl3) δ8.72–8.61(m,1H),8.03(dd,J=7.2,1.0Hz,1H),7.89(m,2H),7.55(m,4H),7.47–7.32(m,18H),7.30–7.24(m,2H),5. 11(d,J=10.4Hz,1H),5.02(d,J=10.9Hz,1H),4.98–4.89(m,3H),4.78(d,J=9.6Hz,1H),4.72–4.54(m,3H),3.84–3.68(m,5H),3.49(m,1H). 13 C NMR (101MHz, CDCl3) δ138.6,138.4,138.2,134.1,134.0,132.4,131.2,128.9,128.6,128.5,128.4,128.3,128.0,127 .9,127.8,127.6,126.7,126.3,126.1,125.8,88.4,87.0,81.7,79.2,78.0,75.9,75.7,75.1,73.6,69.1.IR(neat,cm -1 )3030,2899,2866,1734,1541,1506,1456,1361,1085,1066,1051,1041,769,750,729,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 44 H 42 O5SNa705.2651,Found 705.2640.Mp:85.6–86.9℃.

[0267] Example 61

[0268]

[0269] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (207.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction was spin-dried and column chromatography yielded 5z (121.6 mg, 89%) as a brown solid. 1 H NMR(400MHz, CDCl3)δ8.21(s,1H),7.87(d,J=7.8Hz,1H),7.78(s,2H),7.75–7.69(m,1H),7.57–7.48(m,4H),7 .48–7.35(m,16H),7.32(m,2H),5.00(m,4H),4.91–4.84(m,2H),4.71(m,3H),3.96–3.76(m,4H),3.67(m,2H). 13 C NMR (101MHz, CDCl3) δ138.5,138.4,138.2,133.7,132.6,131.2,131.1,129.6,128.5,128.3,128.0,127 .9,127.8,127.7,126.6,126.3,87.6,87.0,81.0,79.3,77.9,75.9,75.5,75.2,73.6,69.2.IR(neat,cm -1 )2899,2866,1506,1496,1454,1350,1284,1211,1132,1056,1026,734,683.Mp:84.3–85.7℃.

[0270] Example 62

[0271]

[0272] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (252.2 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5aa (103.0 mg, 68%) as a yellow solid. 1H NMR (400MHz, CDCl3) δ8.81(d,J=9.2Hz,1H),8.41(d,J=8.0Hz,1H),8.15(m,2H),8.08–7.95(m,6H),7.47(d,J =6.7Hz,2H),7.39–7.10(m,17H),5.04(d,J=10.4Hz,1H),4.83(m,5H),4.62–4.42(m,4H),3.74–3.62(m,5H). 13 C NMR (101MHz, CDCl3) δ138.5,138.3,138.2,138.1,132.5,132.4,131.4,131.3,131.0,128.5,128.4,128.3,128.2,128.1,128.0,127 .9,127.8,127.7,127.6,127.3,126.2,125.5,125.4,125.0,88.9,86.9,81.6,79.3,77.9,75.8,75.7,75.1,73.5,69.1.IR(neat,cm -1 )3030,2908,2860,2358,2345,1558,1521,1508,1456,1136,1062,1028,839,754,729,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 50 H 44 O5SNa 779.2807,Found779.2793.Mp:106.4–107.9℃.

[0273] Example 63

[0274]

[0275] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (255.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 column chromatography afforded 5ab (117.5 mg, 77%) as a bright yellow solid. 1H NMR (400MHz, CDCl3) δ8.28(m,1H),8.23–8.16(m,1H),8.13–7.89(m,2H),7.77–7.65(m,2H),7.49(t,J=7.9H z,1H),7.37–7.10(m,20H),5.05(d,J=10.1Hz,1H),4.96–4.80(m,4H),4.76–3.97(m,5H),3.86–3.51(m,5H). 13 C NMR (101MHz, CDCl3) δ183.5,182.9,143.0,138.4,138.2,138.0,137.8,135.1,134.3,134.0,133.8,133.5,132.6,132.2,129.5, 128.6,128.5,128.4,128.0,127.9,127.8,126.9,124.4,87.0,84.6,82.7,81.3,79.3,78.1,76.0,75.2,73.6,69.4.IR(neat,cm -1 )2866,1670,1653,1558,1541,1508,1456,1313,1269,1124,1085,1062,1028,958,748,729,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 48 H 42 O7SNa 785.2549,Found 785.2532.Mp:147.9–148.9℃.

[0276] Example 64

[0277]

[0278] To a reaction tube, sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (208.3 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL) were added and reacted at 25°C for 16 hours. After completion, the reaction was spin-dried and column chromatography afforded 5ac (131.3 mg, 96%) as a white solid. 1H NMR(400MHz, CDCl3) δ8.85(d,J=3.8Hz,1H),8.05(s,1H),7.99(d,J=8.8Hz,1 H),7.85(d,J=8.8Hz,1H),7.78(d,J=8.2Hz,1H),7.39(d,J=7.3Hz,2H),7.37– 7.25(m,17H),7.21(d,J=6.9Hz,2H),4.94–4.82(m,4H),4.77(dd,J=15.6,9.9 Hz,2H),4.58(m,3H),3.83(d,J=10.6Hz,1H),3.79–3.64(m,3H),3.57(m,2H). 13 C NMR (101MHz, CDCl3) δ150.4,147.2,138.4,138.2,138.0,135.8,132.8,132.7,129.9,129.7,128.6,128.5, 128.2,128.0,127.9,127.8,121.6,87.2,86.8,80.9,79.2,77.8,75.9,75.5,75.1,73.6,69.2.IR(neat,cm -1 )2902,2868,1489,1454,1352,1282,1132,1085,1060,1028,985,827,746,692.HRMS(ESI)m / z:[M+H] + Calcd for C 43 H 42 NO5S684.2784,Found 684.2760.Mp:93.2–94.4℃.

[0279] Example 65

[0280]

[0281] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (208.9 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction was evaporated to dryness and column chromatography afforded 5ad (126.0 mg, 92%) as a white solid. 1H NMR(400MHz, CDCl3)δ8.79(s,2H),8.25(s,1H),7.95(m,2H),7.42–7.24(m,18H),7.2 3–7.15(m,2H),4.98–4.72(m,6H),4.68–4.48(m,3H),3.87–3.70(m,4H),3.63(m,2H). 13 C NMR (101MHz, CDCl3) δ145.4,144.7,143.1,142.0,138.4,138.1,138.0,137.8,132.3,129.7,129.4,128.5,128 .4,128.2,128.0,127.9,127.8,127.6,86.7,86.5,80.9,79.3,77.8,75.9,75.6,75.1,73.5,68.9.IR(neat,cm -1 )2902,2866,1600,1496,1454,1361,1132,1058,1028,987,746,734,692.HRMS(ESI)m / z:[M+H] + Calcd for C 42 H 41 N2O5S 685.2736,Found 685.2726.Mp:73.6–74.7℃.

[0282] Example 66

[0283]

[0284] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (181.8 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction was evaporated to dryness and column chromatography afforded 5ae (75.5 mg, 59%) as a yellow liquid. 1 H NMR(400MHz, CDCl3)δ7.72(d,J=3.4Hz,1H),7.35(m,2H),7.32–7.21(m,17H) ,7.20–7.14(m,2H),4.98–4.71(m,6H),4.62–4.48(m,3H),3.78–3.54(m,6H). 13C NMR (101MHz, CDCl3) δ160.1,142.9,138.4,138.3,138.1,137.8,128.5,128.4,127.9,127 .8,127.6,121.6,86.6,85.9,80.6,79.6,77.6,75.9,75.5,75.1,73.5,68.8.IR(neat,cm -1 )2866,1496,1454,1361,1209,1068,1026,910,732,692.HRMS(ESI)m / z:[M+H] + Calcd for C 37 H 38 NO5S2640.2191,Found 640.2168.

[0285] Example 67

[0286]

[0287] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (178.3 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5af (116.6 mg, 92%) as a white solid. 1 H NMR (400MHz, CDCl3) δ8.74(s,1H),8.46(s,1H),7.91(d,J=8.0Hz,1H),7.39–7.22(m,17H),7.20(s,1H) ,7.19–7.14(m,2H),7.07(m,1H),4.91–4.73(m,5H),4.66–4.45(m,4H),3.69(m,4H),3.52–3.41(m,2H). 13 CNMR (101MHz, CDCl3) δ152.2,148.5,140.0,138.4,138.2,138.0,137.9,128.5,128.2,128.0,127.9 ,127.8,127.7,123.8,87.0,86.7,81.0,79.2,77.7,77.4,75.9,75.6,75.1,73.5,68.9.IR(neat,cm -1)2904,1558,1456,1355,1132,1060,1053,1029,983,752,732,692.HRMS(ESI)m / z:[M+H] + Calcd for C 39 H 40 NO5S 634.2627,Found634.2606.Mp:77.8–78.4℃.

[0288] Example 68

[0289]

[0290] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (220.2 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5ag (121.0 mg, 84%) as a white solid. 1 H NMR (400MHz, CDCl3) δ8.58 (s, 1H), 7.47–7.07 (m, 20H), 6.03 (d, J = 10.1Hz, 1H),4.93(m,5H),4.74–4.34(m,4H),4.20–4.05(m,1H),3.97–3.66(m,5H). 13 C NMR (101MHz, CDCl3) δ166.6,156.0,153.4,149.3,143.2,142.7,138.6,138.3,138.0,128.4,128.3,128 .1,127.9,127.8,127.7,127.5,87.0,81.2,81.1,79.4,77.9,75.8,75.5,75.0,73.4,68.8.IR(neat,cm -1 )2866,2362,1585,1516,1508,1489,1456,1369,1338,1085,1066,1028,825,763,750,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 38 H 36 Cl2N2O5S 725.1620,Found 725.1635.Mp:95.8–96.7℃.

[0291] Example 69

[0292]

[0293] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (216.1 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5ah (112.9 mg, 81%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.34(dd,J=7.8,1.5Hz,2H),7.31–7.22(m,18H),7.19(dd,J=7.4,1.8Hz,2H),4.95–4.79(m,5H),4. 72(d,J=10.2Hz,1H),4.58(d,J=10.9Hz,1H),4.50(q,J=11.8Hz,2H),3.82(s,3H),3.79–3.70(m,2H),3.68–3.55(m,4H). 13 C NMR (101MHz, CDCl3) δ162.4,140.9,138.4,138.3,138.0,137.8,131.2,128.7,128.5,128.4,128.0 ,127.8,127.7,124.2,86.8,85.1,81.2,79.3,77.9,75.9,75.8,75.2,73.5,69.2,52.1.IR(neat,cm -1 )2902,2866,2358,2341,2331,1707,1498,1355,1208,1132,1064,1028,987,765,734,683.HRMS(ESI)m / z:[M+Na] + Calcdfor C 40 H 40 O7S2Na 719.2113,Found 719.2092.Mp:105.4–106.2℃.

[0294] Example 70

[0295]

[0296] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (312.2 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL) were added to a reaction tube and reacted at 25°C for 16 hours. After the reaction was complete, the product was spin-dried and purified by column chromatography to afford 5ai (166.3 mg, 97%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.59 (d, J = 8.4Hz, 2H), 7.44–7.28 (m, 17H), 7.27–7.09 (m, 8H), 6.75 (s, 1H), 4.93 (d, J=6.4Hz,2H),4.91–4.83(m,2H),4.75(m,2H),4.66–4.53(m,3H),3.74(m,4H),3.55(m,2H),2.36(s,3H). 13 C NMR (101MHz, CDCl3) δ144.8,139.3,138.5,138.4,138.1,138.0,137.9,134.7,131.9,129.5,128.7,128.5, 128.2,128.0,127.7,126.2,125.8,105.5,87.1,86.7,80.8,79.1,77.8,75.8,75.6,75.2,73.5,68.9,21.3. 19 F NMR(376MHz,CDCl3)δ-62.13(s).IR(neat,cm -1 )2868,2360,1496,1471,1454,1375,1274,1234,1159,1130,1087,1064,975,908,825,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 51 H 47 F3N2O5SNa 879.3055,Found879.3039.Mp:97.8–98.6℃.

[0297] Example 71

[0298]

[0299] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (192.1 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 5aj (77.5 mg, 59%) as a yellow liquid. 1 H NMR(400MHz, CDCl3)δ7.65(s,1H),7.52(m,3H),7.41–7.20(m,19H),7.16(t ,J=7.8Hz,1H),5.07(d,J=11.4Hz,1H),4.89(t,J=12.5Hz,2H),4.82–4.70(m ,3H),4.67–4.54(m,3H),4.15(s,1H),3.97(t,J=9.5Hz,1H),3.85(d,J=10.8 Hz,1H),3.76(m,1H),3.66(d,J=9.3Hz,1H),3.61–3.52(m,1H),3.03(s,1H). 13 C NMR (101MHz, CDCl3) δ138.5,138.2,138.1,136.2,133.8,130.9,130.7,128.9,128.5,128.4,128.3,128.1,128.0,12 7.9,127.8,127.7,127.4,122.8,87.4,84.3,83.0,80.2,77.7,77.5,75.2,75.1,74.9,73.5,72.7,69.7.IR(neat,cm -1 )2862,1496,1454,1361,1274,1064,1026,908,840,788,731,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 40 O5SNa679.2494,Found 679.2472.

[0300] Example 72

[0301]

[0302] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (192.1 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5ak (52.5 mg, 40%) as a yellow solid. 1 H NMR(400MHz, CDCl3)δ7.67(t,J=1.5Hz,1H),7.59–7.52(m,1H),7.39–7.20(m ,21H),7.08(t,J=7.8Hz,1H),4.95(d,J=11.6Hz,1H),4.77(q,J=10.2Hz,2H), 4.71(d,J=1.3Hz,2H), 4.62(dd,J=12.4,10.7Hz,2H), 4.43(q,J=11.7Hz,2H), 3.96(d,J=2.7Hz,1H),3.92(t,J=9.4Hz,1H),3.67–3.55(m,4H),3.00(s,1H). 13 C NMR (101MHz, CDCl3) δ138.8,138.3,137.9,134.7,131.9,130.7,128.7,128.5,128.4,128.3,128.0 ,127.8,127.6,122.8,87.6,84.2,83.1,77.7,77.5,75.7,74.5,73.6,73.6,72.8,68.8.IR(neat,cm -1 )2868,2360,1496,1454,1359,1145,1116,1045,1026,908,873,750,742,696.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 40 O5SNa679.2494,Found 679.2469.Mp:64.2–65.7℃.

[0303] Example 73

[0304]

[0305] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (326.0 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction is dried and purified by column chromatography to afford 5al (174.2 mg, 99%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.48(d,J=8.6Hz,1H),7.40(d,J=8.6Hz,1H),7.30–7.12(m,22H),7.06(m,3H),6.87(d,J=8.6Hz,1H),6.53(d,J=8. 6Hz,1H),5.15–4.91(m,2H),4.71(m,5H),4.54–4.36(m,5H),3.68–3.33(m,5H),2.30–2.15(m,1H),2.09–1.98(m,1H),1.96–1.78(m,2H). 13 C NMR (101MHz, CDCl3) δ171.2,155.0,154.3,150.4,150.0,138.5,138.3,138.1,136. 7,136.4,133.5,133.4,131.2,131.1,128.6,128.5,128.3,128.1,128.0,127.9,127 .8,127.7,122.1,121.8,87.7,86.8,80.9,79.1,77.8,77.5,75.9,75.5,75.2,73.5 ,69.0,67.4,67.2,60.5,59.5,59.0,47.2,46.6,31.2,30.1,24.6,23.7.IR(neat,cm -1 )2868,1766,1705,1489,1452,1413,1274,1261,1199,1132,1078,1064,1028,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 53 H 53 O9SNNa 902.3339,Found 902.3331.Mp:62.4–63.1℃.

[0306] Example 74

[0307]

[0308] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (337.4 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction is evaporated to dryness and column chromatography yields 5am (120.5 mg, 67%) as a white solid. 1 H NMR (400MHz, CDCl3) δ8.15(d,J=2.1Hz,1H),7.81(d,J=7.6Hz,1H),7.51(d, J=8.6Hz,2H),7.47–7.33(m,4H),7.30(d,J=7.4Hz,2H),7.27–7.16(m,15H) ,7.11(m,3H),6.99(d,J=8.4Hz,1H),6.87(d,J=8.6Hz,2H),5.08(s,2H),4. 75(m,6H),4.59–4.42(m,5H),3.78(s,2H),3.72–3.52(m,6H),3.40(m,2H). 13 C NMR (101MHz, CDCl3) δ191.0,169.8,160.8,150.3,140.5,138.4,138.3,13 8.0,136.4,135.6,133.5,133.0,132.7,131.1,129.6,129.4,128.6,128. 5,128.3,128.1,127.9,127.8,127.2,125.3,122.1,121.4,87.7,86.8,80 .9,79.0,77.8,77.4,75.9,75.6,75.2,73.7,73.5,68.9,40.4.IR(neat,cm -1 )2868,1755,1645,1489,1298,1284,1170,1132,1066,1026,997,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 56 H 50 O9SNa 921.3073,Found 921.3075.Mp:85.7–86.9℃.

[0309] Example 75

[0310]

[0311] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (352.4 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). Incubate at 25°C for 16 hours. After completion, the reaction is dried and purified by column chromatography to afford 5an (136.8 mg, 74%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.57–7.52(m,2H),7.50–7.45(m,4H),7.28(dd,J=9.3,2.5Hz,2H),7.25–7.13(m,21H),7.10–7.05(m,3H),6. 88(d,J=8.7Hz,2H),4.84–4.61(m,5H),4.48(m,4H),3.70–3.51(m,4H),3.38(m,2H),3.18(t,J=7.2Hz,2H),3.04(t,J=7.2Hz,2H). 13 C NMR (101MHz, CDCl3) δ170.5,161.6,150.3,145.7,138.5,138.3,138.1,135.2,133.6,132.4,131.1,129.0,128.8,128.7,128.6,128.5,128. 3,128.1,128.0,127.9,127.8,127.7,126.6,122.2,87.7,86.8,81.0,79.1,77.8,77.5,75.9,75.6,75.2,73.5,69.0,31.3,23.6.IR(neat,cm -1 )2868,1747,1496,1487,1454,1361,1350,1274,1267,1205,1165,1149, 1087,1066,1026,993,885,831,763,748,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 58 H 54 O8SN 924.3570,Found 924.3557.Mp:90.4–91.7℃.

[0312] Example 76

[0313]

[0314] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (347.6 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5ao (135.6 mg, 74%) as a white solid. 1 H NMR (400MHz, CDCl3) δ8.21(d,J=8.5Hz,2H),7.86(d,J=8.5Hz,2H),7.57(d,J=8.7Hz,2 H),7.33–7.28(m,2H),7.27–7.14(m,15H),7.13(s,1H),7.12–7.07(m,2H),6.99(d,J= 8.7Hz,2H),4.85–4.77(m,3H),4.76–4.64(m,2H),4.51(m,4H),3.73–3.53(m,4H),3.4 7–3.39(m,2H),3.04(dd,J=8.6,6.7Hz,4H),1.54–1.42(m,4H),0.80(t,J=7.4Hz,6H). 13 C NMR (101MHz, CDCl3) δ163.7,150.2,145.1,138.4,138.3,138.1,138.0,133.5,132.7,131.6,130.9,128.5,128.4,128.3,128.0,1 27.9,127.8,127.6,127.3,122.0,87.6,86.8,80.9,79.1,77.8,77.4,75.9,75.5,75.1,73.5,69.0,50.0,22.0,11.3.IR(neat,cm -1 )1741,1487,1454,1344,1274,1259,1199,1157,1066,1014,991,908,875,746,696,599,557.HRMS(ESI)m / z:[M+Na] + Calcd for C 53 H 57 O9SNNa938.3372,Found 938.3370.Mp:74.9–75.3℃.

[0315] Example 77

[0316]

[0317] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (300.0 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 5ap (123.9 mg, 74%) as a yellow liquid. 1 H NMR(400MHz, CDCl3)δ7.44(d,J=8.6Hz,2H),7.25(d,J=6.6Hz,2H),7.22–7.11 (m,18H),7.07(m,2H),7.05–7.01(m,2H),6.74(d,J=8.7Hz,2H),4.70(m,5H), 4.53–4.36(m,4H),3.79(m,1H),3.67–3.47(m,4H),3.36(t,J=9.1Hz,2H),2.3 5(d,J=7.2Hz,2H),1.75(m,1H),1.47(d,J=7.1Hz,3H),0.79(d,J=6.6Hz,6H). 13 C NMR (101MHz, CDCl3) δ171.9,149.5,139.8,137.4,137.2,137.0,136.1,132.4,129.7,128.5,127.4,127.3,127.1,126.9,126.8,126 .7,126.6,126.5,126.2,120.9,86.5,85.7,79.8,77.9,76.7,74.7,74.3,74.0,72.3,67.9,44.2,44.0,29.1,21.4,17.5.IR(neat,cm -1 )2868,2360,1747,1454,1361,1274,1201,1153,1083,1068,1028,910,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 53 H 56 O7SNa 859.3644,Found859.3629.

[0318] Example 78

[0319]

[0320] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (366.0 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 5aq (121.2 mg, 64%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ8.13(d,J=2.1Hz,1H),8.04(dd,J=8.8,2.1Hz,1H),7.56(d,J =8.6Hz,2H),7.30(d,J=6.8Hz,2H),7.22(m,17H),7.13–7.08(m,2H),6.99(d,J=8.6 Hz,2H),6.92(d,J=8.9Hz,1H),4.85–4.64(m,5H),4.51(m,4H),3.80(d,J=6.5Hz,2H ),3.72–3.52(m,4H),3.42(m,2H),2.74(s,3H),2.11(m,1H),1.00(d,J=6.7Hz,6H). 13 C NMR (101MHz, CDCl3) δ168.3,163.1,162.8,160.1,149.9,138.5,138.3,13 8.1,138.0,133.5,132.8,132.3,131.6,128.5,128.2,128.0,127.9,127. 8,127.6,125.8,122.1,120.5,115.4,112.8,103.2,87.6,86.8,81.0,79. 1,77.8,75.9,75.8,75.5,75.1,73.5,69.0,28.2,19.1,17.8.IR(neat,cm -1 )1735,1508,1483,1452,1390,1371,1276,1195,1055,1014,763,748,694.HRMS(ESI)m / z:[M+H] + Calcd for C 56 H 55 O8S2N2947.3400,Found 947.3395.

[0321] Example 79

[0322]

[0323] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (367.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5ar (132.9 mg, 70%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.79–7.73(m,2H),7.71–7.64(m,2H),7.57(d,J=8.7Hz,2H ),7.44–7.39(m,2H),7.35(d,J=6.8Hz,2H),7.33–7.23(m,16H),7.17(dd,J=7.3 ,2.0Hz,2H),6.97(d,J=8.8Hz,2H),6.84(d,J=8.7Hz,2H),4.91–4.77(m,4H),4. 72(d,J=10.3Hz,1H),4.56(m,4H),3.69(m,4H),3.53–3.42(m,2H),1.80(s,6H). 13 C NMR (101MHz, CDCl3) δ194.2,172.2,159.5,145.0,138.5,138.4,138.3,138.0,136.4,133.4,132.2,131.2,128.6,128.5,12 8.4,128.2,128.0,127.8,121.7,117.4,87.5,86.7,80.9,79.5,79.0,77.8,75.9,75.5,75.1,73.4,69.0,25.5.IR(neat,cm -1 )1761,1653,1597,1274,1261,1114,1089,1066,1053,927,887,763,750.HRMS(ESI)m / z:[M+Na] + Calcd for C 57 H 53 O9SClNa 971.2997,Found 971.2970.Mp:92.4–93.7℃.

[0324] Example 80

[0325]

[0326] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (326.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 afforded 5as (123.4 mg, 70%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.50 (d, J=8.7Hz, 2H), 7.31–7.26 (m, 2H), 7.25–7.14 (m, 15H), 7.09 (m,2H),7.06(s,1H),6.89(d,J=7.4Hz,1H),6.82–6.76(m,2H),6.55(d,J=7.5Hz,1H),6.5 2(s,1H),4.84–4.69(m,4H),4.64(d,J=10.4Hz,1H),4.56–4.38(m,4H),3.87(s,2H),3.62 (m,4H),3.44–3.34(m,2H),2.19(s,3H),2.08(s,3H),1.77(d,J=2.4Hz,4H),1.26(s,6H). 13 C NMR (101MHz, CDCl3) δ176.2,157.0,150.8,138.6,138.4,138.2,136.6,13 3.6,130.8,130.5,128.6,128.5,128.3,128.1,128.0,127.9,127.8,127.7 ,123.7,122.2,120.9,112.1,87.7,86.8,81.0,79.1,77.9,77.4,75.9,75 .5,75.2,73.5,69.1,67.9,42.6,37.3,25.4,25.3,21.6,16.0.IR(neat,cm -1 )1749,1489,1454,1274,1261,1199,1163,1157,1111,1085,1064,1028,750,729,696.HRMS(ESI)m / z:[M+Na] + Calcd for C 55 H 60 O8SNa 903.3907,Found 903.3889.

[0327] Example 81

[0328]

[0329] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (326.7 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 was performed to yield 5at (195.7 mg, 99%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.53 (d, J = 8.6 Hz, 2H), 7.46 (d, J = 8.7 Hz, 2H), 7.32 (d, J = 8. 6Hz,2H),7.27–7.23(m,2H),7.22–7.12(m,14H),7.07(m,4H),6.93(d,J=2.5Hz,1 H),6.79(dd,J=13.4,8.9Hz,3H),6.61–6.52(m,1H),4.77–4.61(m,5H),4.51–4.4 0(m,4H),3.76(s,2H),3.69(s,3H),3.59(m,4H),3.40–3.32(m,2H),2.33(s,3H). 13 C NMR (101MHz, CDCl3) δ169.1,168.3,156.3,150.4,139.4,138.5,138.3,138.1,136.3,133.9,133.5,131.3,129.2,128.5,128.4,128.2,128. 0,127.9,127.8,122.0,115.1,112.0,111.9,101.3,87.6,86.8,80.9,79.1,77.8,75.9,75.5,75.1,73.5,69.0,55.8,30.6,13.5.IR(neat,cm -1 )1749,1676,1463,1454,1317,1274,1267,1261,1159,1130,1087,1064,1028,763,748,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 59 H 54 O9SClNNa1010.3106,Found 1010.3083.Mp:73.8–74.5℃.

[0330] Example 82

[0331]

[0332] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea reagent (392.4 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). React at 25°C for 16 hours. After the reaction is complete, the product is dried and purified by column chromatography to afford 5au (148.9 mg, 75%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.65–7.59(m,4H),7.41(m,2H),7.39–7.28(m,17H),7.26(s,1H),7.25–7.21(m,2H),7.15(d,J=8.6Hz,2H),6.98–6.9 0(m,4H),6.23(t,J=5.5Hz,1H),4.96–4.74(m,5H),4.61(m,4H),3.83–3.62(m,6H),3.57–3.48(m,2H),2.89(t,J=6.9Hz,2H),1.77(s,6H). 13 C NMR (101MHz, CDCl3) δ172.7,166.4,154.1,150.2,138.4,138.3,138.1,138 .0,137.7,133.3,133.0,132.9,131.5,129.7,128.9,128.5,128.4,128.3, 128.2,128.0,127.9,127.8,127.6,121.8,119.6,87.6,86.7,80.9,79.3,7 9.0,77.8,77.4,75.9,75.5,75.1,73.4,69.1,41.3,34.8,25.5.IR(neat,cm -1 )1755,1645,1508,1487,1274,1267,1118,1085,1066,1028,1014,908,884,748,731,696.HRMS(ESI)m / z:[M+H] + Calcd for C 59 H 59 O9SNCl 992.3599,Found992.3590.Mp:73.1–74.4℃.

[0333] Example 83

[0334]

[0335] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (349.4 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 5av (182.0 mg, 99%) as a colorless liquid. 1 H NMR(400MHz, CDCl3)δ8.00(d,J=8.4Hz,2H),7.63(d,J=8.4Hz,2H),7.44–7.31(m,17 H),7.28–7.22(m,3H),5.00–4.74(m,6H),4.72–4.55(m,4H),4.51(d,J=2.5Hz,1H), 4.38(d,J=11.8Hz,1H),4.30(d,J=8.0Hz,1H),4.01(d,J=12.9Hz,1H),3.89–3.69(m ,5H),3.62(dd,J=11.8,6.1Hz,2H),1.59(s,3H),1.52(s,3H),1.39(d,J=4.5Hz,6H). 13 C NMR (101MHz, CDCl3) δ165.6,141.5,138.4,138.1,138.0,137.8,129.6,128.6,128.5,128.3,128.1,128.0,127.8,109.2,108.9,101. 7,86.7,86.4,80.8,79.2,77.7,77.5,75.9,75.7,75.2,73.5,70.8,70.6,70.2,68.9,65.4,61.4,26.6,26.0,25.6,24.1.IR(neat,cm -1 )2868,1722,1595,1454,1375,1271,1251,1105,1130,1028,1016,752,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 53 H 58 O 12 SNa941.3547,Found 941.3529.

[0336] Example 84

[0337]

[0338] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylarylthiourea (293.0 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (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 5aw (113.9 mg, 69%) as a yellow liquid. 1 H NMR(400MHz, CDCl3)δ7.79(d,J=8.5Hz,2H),7.47(d,J=8.4Hz,2H),7.28–7.15(m,11H),7 .12(s,1H),7.09(dd,J=7.3,2.0Hz,2H),5.23(s,1H),4.72(m,6H),4.47(m,3H),4.28(m, 2H),4.05(d,J=4.8Hz,1H),3.73–3.54(m,4H),3.50–3.41(m,2H),2.43–2.28(m,2H),2.1 9–2.12(m,3H),2.05(d,J=12.9Hz,1H),1.74(d,J=10.8Hz,1H),1.18(s,3H),1.09(s,3H). 13 C NMR (101MHz, CDCl3) δ166.1,140.9,139.6,138.4,138.1,138.0,137.8,130.1,129.7,128.6,128.5,128.3,128.0,127.8,123. 1,86.7,86.5,83.1,80.8,79.2,77.7,77.4,75.9,75.6,75.2,73.5,68.9,63.4,60.5,42.0,35.1,34.8,30.6,25.6.IR(neat,cm -1 )1714,1454,1361,1274,1261,1107,1085,1064,906,763,748,727,696.HRMS(ESI)m / z:[M+Na] + Calcd for C 52 H 56 O7SNa847.3644,Found 847.3629.

[0339] Example 85

[0340]

[0341] A glucosinolate compound (63.3 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (1 mL) were added to a reaction tube and reacted at 25°C for 8 hours. After the reaction was complete, the mixture was dried and column chromatography was performed to obtain a colorless liquid 6a (56.5 mg, 85%). 1 H NMR(400MHz, CDCl3) δ7.87(d,J=7.8Hz,2H),7.49(d,J=7.2Hz,1H),7.36(m,4H),7.25(m,10H) ,7.21–7.17(m,4H),7.17–7.12(m,2H),7.11–7.07(m,2H),5.03(d,J=9.6Hz,1H),4.86(d,J=11 .0Hz,1H),4.82–4.68(m,3H),4.49(d,J=10.9Hz,1H),4.35(d,J=9.4Hz,1H),4.28(q,J=12.0H z,2H),4.02(t,J=9.1Hz,1H),3.69(t,J=9.0Hz,1H),3.49(m,3H),3.28(dd,J=9.6,3.2Hz,1H). 13 C NMR (101MHz, CDCl3) δ138.16,138.00,137.70,137.52,137.10,133.97,133.86,130.29,129.90,129.72,128.76,128.57, 128.51,128.48,128.42,128.06,127.71,127.64,91.07,86.27,79.66,77.61,76.94,76.01,75.54,75.17,73.49,68.58.

[0342] Example 86

[0343]

[0344] A glucosinolate compound (65.1 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (1 mL) were added to a reaction tube and reacted at 25°C for 8 hours. After the reaction was complete, the mixture was dried and column chromatography was performed to obtain a colorless liquid 6b (60.8 mg, 89%). 1H NMR (400MHz, DMSO) δ7.71(d,J=7.9Hz,2H),7.56(t,J=8.1Hz,2H),7.33(m,1 6H),7.22(m,4H),5.03(d,J=8.6Hz,1H),4.94(d,J=10.3Hz,1H),4.86–4.78 (m,3H),4.73(d,J=11.0Hz,1H),4.55(d,J=11.1Hz,1H),4.32(q,J=12.0Hz, 2H),3.95–3.85(m,2H),3.69–3.61(m,1H),3.59(s,1H),3.54–3.46(m,3H). 13 C NMR (101MHz, DMSO) δ166.56,128.74,128.70,128.64,128.55,128.36,128.28,128. 00,127.93,116.63,89.68,85.38,78.77,77.87,77.54,75.35,74.59,72.75,66.81.

[0345] Example 87

[0346]

[0347] A glucosinolate (65.7 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (1 mL) were added to a reaction tube and allowed to react at 25°C for 8 hours. After the reaction was complete, the mixture was dried and column chromatography afforded a colorless liquid 6c (63.4 mg, 92%). 1 H NMR (400MHz, CDCl3) δ7.71(d,J=7.6Hz,1H),7.63(d,J=8.1Hz,1H),7.48(d,J=7.0Hz,2H),7.42–7. 26(m,18H),7.23–7.17(m,2H),5.15(d,J=9.7Hz,1H),4.99(d,J=11.0Hz,1H),4.95–4.81(m,3H),4 .61(d,J=10.8Hz,1H),4.51–4.45(m,2H),4.40(d,J=12.0Hz,1H),4.17(t,J=9.1Hz,1H),3.82(t,J =9.0Hz,1H),3.70–3.58(m,2H),3.53(d,J=11.0Hz,1H),3.41(dd,J=9.7,3.6Hz,1H),3.19(s,1H). 13C NMR (101MHz, CDCl3) δ138.13,137.95,137.64,137.54,137.45,137.25,128.82,128.74,128.58,128.52,128.50,128.43,128.36,128.09 ,128.02,127.87,127.74,127.71,127.69,123.25,91.09,86.19,81.69,79.68,79.61,77.50,76.89,76.02,75.57,75.20,73.68,68.60.

[0348] Example 88

[0349]

[0350] A glucosinolate compound (70.1 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (1 mL) were added to a reaction tube and reacted at 25°C for 8 hours. After the reaction was complete, the mixture was dried and column chromatography was performed to obtain a colorless liquid 6d (66.0 mg, 90%). 1 H NMR (400MHz, CDCl3) δ8.00(s,1H),7.90(d,J=7.7Hz,1H),7.51(d,J=8.0Hz,1H),7.35(d,J=7.9Hz,1H),7.26–7.18(m,18H),7.08–7.04(m,2H), 5.16(d,J=3.3Hz,1H),4.86(t,J=9.7Hz,1H),4.79–4.59(m,5H),4.45(m,4H),3.98(d,J=9.9Hz,1H),3.91(t,J=9.3Hz,1H),3.58–3.53(m,2H). 13 C NMR (101MHz, CDCl3) δ138.65,138.16,137.83,137.79,134.70,133.83,130.28,129.87,128.55,128.46,128.43,128.34, 128.24,128.12,128.04,128.01,127.94,127.79,127.70,81.75,79.94,77.70,75.79,75.07,73.51,73.29,70.27,68.56.

[0351] Example 89

[0352]

[0353] A glucosinolate (67.7 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (1 mL) were added to a reaction tube and allowed to react at 25°C for 8 hours. After the reaction was complete, the mixture was dried and column chromatography afforded the colorless liquid 6e (62.4 mg, 88%). 1 H NMR(400MHz, CDCl3)δ7.55(dd,J=8.2,1.3Hz,1H),7.47(d,J=7.0Hz,2H),7.40–7.29(m,15H),7 .29–7.24(m,2H),7.23–7.19(m,2H),6.85(d,J=8.2Hz,1H),5.96(d,J=11.7Hz,2H),5.12(d,J=9 .6Hz,1H),4.98(d,J=11.0Hz,1H),4.94–4.79(m,3H),4.60(d,J=10.9Hz,1H),4.50–4.35(m,3H ),4.10(t,J=9.1Hz,1H),3.80(t,J=9.1Hz,1H),3.66–3.57(m,3H),3.43(dt,J=9.6,3.1Hz,1H). 13 C NMR (101MHz, CDCl3) δ152.57,147.94,138.16,138.05,137.67,137.52,130.15,128.73,128.56,128.51,128.47,128.42,128.06,128 .00,127.85,127.70,127.56,125.86,109.83,108.13,102.39,91.19,86.28,79.76,77.68,76.99,76.00,75.49,75.17,73.58,68.81.

[0354] Example 90

[0355]

[0356] A glucosinolate (69.7 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (1 mL) were added to a reaction tube and allowed to react at 25°C for 8 hours. After the reaction was complete, the mixture was spin-dried and column chromatography afforded 6f (59.7 mg, 82%) as a colorless liquid. 1H NMR (400MHz, CDCl3) δ8.01(s,1H),7.92(d,J=7.8Hz,1H),7.53(d,J=5.1Hz,1H),7. 29(d,J=7.0Hz,2H),7.24–7.18(m,14H),7.09(dd,J=13.1,5.6Hz,4H),5.32(d,J=9 .4Hz,1H),5.00(d,J=10.2Hz,1H),4.89–4.70(m,4H),4.49(d,J=10.9Hz,1H),4.26 –4.09(m,3H),3.80(s,3H),3.77(s,1H),3.49(dd,J=17.3,8.7Hz,2H),3.43(s,2H). 13 C NMR (101MHz, CDCl3) δ160.05,142.05,138.18,138.08,137.80,137.77,131.53,129.24,128.51,128.46,128.34,128 .28,128.26,127.95,127.76,127.61,127.55,91.31,86.38,80.26,77.75,77.26,75.91,75.08,73.36,68.63,53.11.

[0357] 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.

[0358] 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.

[0359] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0360] 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. A tetramethylarylthiourea reagent, characterized in that The structure of the tetramethylarylthiourea reagent is shown in formula (3): in, Ar is selected from a benzene ring, a substituted benzene ring, a heteroaromatic ring, a substituted heteroaromatic ring, and an aromatic ring containing an active molecule; wherein the substituted benzene ring is selected from a halogen-substituted phenyl, an alkyl-substituted phenyl, an ester-substituted phenyl, a nitro-substituted phenyl, an alkynyl-substituted phenyl, a trifluoromethyl-substituted phenyl, a polysubstituted phenyl, anthracene, and naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene, thiazole, and pyridazine; the substituted heteroaromatic ring is selected from a halogen-substituted pyridazine and an ester-substituted thiophene; the active molecule in the aromatic ring containing an active molecule is selected from amino acids, naproxen, telmisartan, podophyllotoxin, isoxacic acid, opsazone, probenecid, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, indomethacin, bezafibrate, and noproxol.

2. A method for synthesizing a tetramethylarylthiourea reagent, characterized in that: The method comprises the following steps: Step 1: Using the aromatic amine represented by formula (1) as a reaction raw material, reacting in a solvent under the action of an activation reagent and tetrafluoroboric acid to obtain a product; Step 2: Add tetramethylthiourea shown in formula (2) to the product obtained in step 1, and react in an organic solvent under the action of a catalyst to obtain a tetramethylarylthiourea reagent shown in formula (3). The reaction process is shown in reaction formula (a): in, Ar is selected from a benzene ring, a substituted benzene ring, a heteroaromatic ring, a substituted heteroaromatic ring, and an aromatic ring containing an active molecule; wherein the substituted benzene ring is selected from a halogen-substituted phenyl, an alkyl-substituted phenyl, an ester-substituted phenyl, a nitro-substituted phenyl, an alkynyl-substituted phenyl, a trifluoromethyl-substituted phenyl, a polysubstituted phenyl, anthracene, and naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene, thiazole, and pyridazine; the substituted heteroaromatic ring is selected from a halogen-substituted pyridazine and an ester-substituted thiophene; the active molecule in the aromatic ring containing an active molecule is selected from amino acids, naproxen, telmisartan, podophyllotoxin, isoxacic acid, opsazone, probenecid, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, indomethacin, bezafibrate, and noproxol.

3. The synthesis method according to claim 2, wherein The activation reagent is selected from one or more of sodium nitrite, hydrochloric acid, and sulfuric acid; and / or the catalyst is selected from one or more of cuprous chloride, cupric chloride, cuprous iodide, and cupric iodide; and / or the solvent is selected from one or more of water, acetone, ethanol, methanol, and tetrahydrofuran; and / or the organic solvent is selected from one or more of acetone, ethanol, methanol, and tetrahydrofuran; and / or the reaction temperature is 0 to 25° C.; and / or the reaction time is 1 to 16 hours; and / or the amount ratio of the activation reagent, the tetrafluoroboric acid, the catalyst, the solvent, the organic solvent, the tetramethylthiourea, and the aromatic amine is (1-2) mole: (1-2) mole: (0.1-1) mole: (5-10) volume: (5-10) volume: 1 mole: (1-2) mole.

4. A use of a tetramethylarylthiourea reagent in the selective construction of glucosidic compounds, characterized in that: The sugar represented by formula (4) and the tetramethylarylthiourea reagent represented by formula (3) are used as reaction raw materials. Under the action of a base, in an organic solvent, a glucosidic compound represented by formula (5) is obtained by reaction. The reaction process is shown in reaction formula (b): in, n is an integer selected from 4 to 6; R 2 is selected from benzyl, acyl, and silicon; Ar is selected from benzene ring, substituted benzene ring, heteroaromatic ring, substituted heteroaromatic ring, and aromatic ring containing active molecules; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ester-substituted phenyl, nitro-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, and naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene, thiazole, and pyridazine; the substituted heteroaromatic ring is selected from halogen-substituted pyridazine and ester-substituted thiophene; the active molecule in the aromatic ring containing active molecules is selected from amino acids, naproxen, telmisartan, podophyllotoxin, isoxacic acid, opsazone, probenecid, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, indomethacin, bezafibrate, and noproxol.

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 ratio of the sugar, the base, the organic solvent, and the tetramethylarylthiourea reagent is 1 mol: (1.5 to 3.1) mol: (5 to 10) volume: (1.5 to 3) mol.

7. Use of a glucosinolate compound in constructing an oxidized glucosinolate compound, characterized in that: The glucosinolate compound represented by formula (5) is used as a reaction raw material, and under the action of an oxidant, in an organic solvent, a reaction is performed to obtain an oxidized glucosinolate compound represented by formula (6). The reaction process is shown in reaction formula (c): in, n is an integer selected from 4 to 6; R 2 is selected from benzyl, acyl, and silicon; Ar is selected from benzene ring, substituted benzene ring, heteroaromatic ring, substituted heteroaromatic ring, and aromatic ring containing active molecules; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ester-substituted phenyl, nitro-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, and naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene, thiazole, and pyridazine; the substituted heteroaromatic ring is selected from halogen-substituted pyridazine and ester-substituted thiophene; the active molecule in the aromatic ring containing active molecules is selected from amino acids, naproxen, telmisartan, podophyllotoxin, isoxacic acid, opsazone, probenecid, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, indomethacin, bezafibrate, and noproxol.

8. The use according to claim 7, characterized in that The ratio of the glucosidic compound represented by formula (5), the organic solvent and the oxidant is 1 mol: (5-10) volume: (2-3) mol; and / or, the organic solvent is selected from one or more of chloroform and dichloromethane; and / or, the oxidant is selected from one or more of m-chloroperbenzoic acid and hydrogen peroxide; and / or, The reaction temperature is 25-70° C.; and / or the reaction time is 8-16 hours.

9. A glucosinolate compound, characterized in that Its structure is shown in formula (5): in, n is an integer selected from 4 to 6; R 2 is selected from benzyl, acyl, and silicon; Ar is selected from benzene ring, substituted benzene ring, heteroaromatic ring, substituted heteroaromatic ring, and aromatic ring containing active molecules; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ester-substituted phenyl, nitro-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, and naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene, thiazole, and pyridazine; the substituted heteroaromatic ring is selected from halogen-substituted pyridazine and ester-substituted thiophene; the active molecule in the aromatic ring containing active molecules is selected from amino acids, naproxen, telmisartan, podophyllotoxin, isoxacic acid, opsazone, probenecid, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, indomethacin, bezafibrate, and noproxol.

10. An oxidized sulfosuccinoside compound, characterized in that: Its structure is shown in formula (6): wherein n is an integer selected from 4 to 6; R 2 is selected from benzyl, acyl, and silicon; Ar is selected from benzene ring, substituted benzene ring, heteroaromatic ring, substituted heteroaromatic ring, and aromatic ring containing active molecules; wherein the substituted benzene ring is selected from halogen-substituted phenyl, alkyl-substituted phenyl, ester-substituted phenyl, nitro-substituted phenyl, alkynyl-substituted phenyl, trifluoromethyl-substituted phenyl, polysubstituted phenyl, anthracene, and naphthalene; the heteroaromatic ring is selected from quinoline, pyridine, thiophene, thiazole, and pyridazine; the substituted heteroaromatic ring is selected from halogen-substituted pyridazine and ester-substituted thiophene; the active molecule in the aromatic ring containing active molecules is selected from amino acids, naproxen, telmisartan, podophyllotoxin, isoxacic acid, opsazone, probenecid, ibuprofen, febuxostat, fenofibric acid, gemfibrozil, indomethacin, bezafibrate, and noproxol.

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