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

Abstract

The invention discloses a tetramethyl alkyl thiourea reagent, a synthesis method thereof and application of the tetramethyl alkyl thiourea reagent in selective construction of thioglycoside compounds, the method takes a compound shown in a formula (1) and an alkyl halide shown in a formula (2) as reaction raw materials, and the tetramethyl alkyl thiourea reagent shown in a formula (3) is obtained through reaction in an organic solvent; the thioglycoside compound is obtained by taking sugar as shown in a formula (4) and a tetramethyl alkyl 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 alkyl 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 tetramethylalkylthiourea reagent and a synthesis method thereof, and application thereof in the selective construction of glucosidoglycoside compounds. Background Art

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

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

[0004] To overcome the limitations of traditional synthesis of glucosinolates, the present invention utilizes a tetramethylalkylthiourea reagent. This reaction is highly efficient and selective, requiring no pre-functionalization of the reaction substrate or the presence of a transition metal. It directly utilizes readily available raw materials to yield diverse, stereospecific glucosinolates. In light of this, the present invention proposes a reaction method for preparing the tetramethylalkylthiourea reagent by reacting an alkyl halide with another molecule of tetramethylthiourea. Furthermore, a reaction method for preparing glucosinolates by reacting the tetramethylalkylthiourea reagent with another molecule of sugar in the presence of a base is also proposed.

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

[0006]

[0007] in,

[0008] R 1 Selected from primary alkyl, secondary alkyl, tertiary alkyl, allyl, propargyl, benzyl, and alkyl containing active molecules; wherein the active molecules are selected from amino acids, isoxacic acid, naproxen, opsaqin, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, and indomethacin;

[0009] X is selected from halogen.

[0010] Preferably, R 1Selected from C1-C6 primary alkyl, C3-C6 secondary alkyl, C6 tertiary alkyl, allyl, propargyl, benzyl and alkyl containing active molecules; wherein the active molecules are selected from amino acids, isoxacic acid, naproxen, opsazone, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, indomethacin; X is selected from fluorine, chlorine, bromine and iodine.

[0011] More preferably, R 1 is selected from methyl, ethyl, n-butyl, n-arginyl, isopropyl, cyclohexyl, allyl, propargyl, benzyl and an alkyl group containing an active molecule; wherein the active molecule is selected from amino acids, isoxacic acid, naproxen, opsazone, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, indomethacin; and X is selected from bromine and iodine.

[0012] Furthermore, the tetramethylalkylthiourea reagent compound represented by formula (3) of the present invention includes the following and Table 1:

[0013]

[0014]

[0015] The present invention also provides a method for synthesizing a tetramethylalkylthiourea reagent, wherein tetramethylthiourea represented by formula (1) and an alkyl halide represented by formula (2) are used as reaction raw materials, and a tetramethylalkylthiourea reagent represented by formula (3) is obtained by reacting in an organic solvent. The reaction process is shown in reaction formula (a);

[0016]

[0017] Among them, R 1 The definitions of X are the same as those in Formula 3.

[0018] In the present invention, in reaction formula (a), the molar ratio of tetramethylthiourea represented by formula (1) to the alkyl halide represented by formula (2) is 1:(2-3); preferably, 1:2;

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

[0020] In the present invention, in reaction formula (a), the volume amount of the organic solvent is 5-20, based on tetramethylthiourea (mole); preferably, it is 10.

[0021] In the present invention, in reaction formula (a), the reaction temperature is 25 to 70°C; preferably, 70°C;

[0022] In the present invention, in reaction formula (a), the reaction time is 8-16 hours; preferably, 16 hours;

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

[0024] The present invention also proposes the use of the tetramethylalkylthiourea reagent in the selective construction of glucosidic compounds, wherein the sugar represented by formula (4) and the tetramethylalkylthiourea reagent represented by formula (3) are used as reaction raw materials, and in the presence of a base, in an organic solvent, a glucosidic compound represented by formula (5) is obtained by reaction, and the reaction process is shown in reaction formula (b):

[0025]

[0026] Among them, R 2 is selected from alkyl, acyl, and silicon; n is an integer selected from 1 to 100; R 1 , X is defined as described in Formula 3;

[0027] Preferably, R 2 is selected from an alkyl group containing an aromatic group, an alkyl acyl group, or a bulky hindered silicon group; n is an integer selected from 1 to 10;

[0028] More preferably, R 2 is selected from benzyl; and n is selected from an integer of 3-4.

[0029] 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);

[0030] 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;

[0031] In the present invention, in reaction formula (b), the reaction temperature is -78 to 50°C; preferably, 25°C;

[0032] In the present invention, in reaction formula (b), the reaction time is 8-24 hours; preferably, 16 hours;

[0033] In the present invention, in reaction formula (b), the molar ratio of the sugar, base and tetramethylalkylthiourea reagent is 1:(1.5-3.1):(1.5-3); preferably, 1:3.1:3;

[0034] In the present invention, in reaction formula (b), the volume amount of the organic solvent is 5-20, based on the sugar (mole); preferably, it is 10.

[0035] In the present invention, in reaction formula (b), the reaction is carried out in an air atmosphere.

[0036] The present invention also provides a glucosidoglycoside compound, the structure of which is shown in formula (5):

[0037]

[0038] Among them, R 1 、R 2 The definition of is the same as that described in reaction formula (b); n is an integer selected from 1-100.

[0039] Preferably, n is selected from an integer of 1-10; more preferably, n is selected from an integer of 3-4.

[0040] Furthermore, the glucosinolate compounds represented by formula (5) of the present invention are as described in Table 2.

[0041] The present invention also proposes the use of the glucosinolate compound in the selective construction of an oxidized glucosinolate compound, wherein the glucosinolate compound shown in 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 shown in formula (6), and the reaction process is shown in reaction formula (c):

[0042]

[0043] Among them, R 1 、R 2 The definition is the same as that described in reaction formula (b); n is an integer selected from 1-100;

[0044] Preferably, n is selected from an integer of 1-10; more preferably, n is selected from an integer of 3-4.

[0045] 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;

[0046] In the present invention, in reaction formula (c), the oxidant is selected from one or more of meta-chloroperbenzoic acid, hydrogen peroxide, etc.; preferably, it is meta-chloroperbenzoic acid;

[0047] In the present invention, in reaction formula (c), the molar ratio of the glucosidic compound represented by formula (5) to the oxidant is 1:(2-3); preferably, 1:2.5;

[0048] In the present invention, in reaction formula (c), the volume amount of the organic solvent is 5-20, based on the mole of the glucosinolate compound; preferably, it is 10.

[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 proposes an oxidized glucosinolate compound, the structural formula of which is shown in formula (6):

[0052]

[0053] Among them, R 1 、R 2 The definition is the same as that described in reaction formula (b); n is an integer selected from 1-100;

[0054] Preferably, R 1 、R 2 The definition is the same as that described in reaction formula (b); n is an integer selected from 1-10;

[0055] More preferably, R 1 、R 2 The definition of is the same as that described in reaction formula (b); n is an integer selected from 3-4.

[0056] Furthermore, the oxidized glucosinolate compounds represented by formula (6) of the present invention are shown in Table 3.

[0057] The present invention also provides a tetramethylalkylthiourea reagent compound as shown in formula (3) prepared according to the above-mentioned synthesis method of the present invention.

[0058] The present invention also proposes that the tetramethylalkylthiourea reagent compound represented by formula (3) can be used as or in the preparation of glucosidoglycoside compounds.

[0059] The present invention also proposes that the glucosinolate compound represented by formula (5) can be used as or for preparing oxidized glucosinolate compounds.

[0060] In a specific embodiment, the synthesis reaction of the present invention is carried out in a reaction flask A, and tetramethylthiourea (1 mmol) represented by formula (1), an alkyl halide (3 mmol) represented by formula (2), and an organic solvent (10 mL) are added to the reaction flask A, and the reaction system is stirred at 70° C. under an air atmosphere for 16 hours; after the reaction is completed, silica gel is added and dried in a spin-drying manner, and the target product, i.e., a tetramethylalkylthiourea reagent represented by formula (3), is obtained by column chromatography.

[0061] 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 tetramethylalkylthiourea 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.

[0062] 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.

[0063] The yields of the tetramethylalkylthiourea reagent compound shown in formula (3) and the glucosidoglycoside compound shown in formula (5) prepared by the synthesis method of the present invention are 55% or more.

[0064] 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 tetramethylalkylthiourea reagent is simple to prepare, stable, and has no irritating odor; and the reaction conditions are relatively mild. The tetramethylalkylthiourea 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

[0065] The present invention is 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 are protected by the appended claims. The process, conditions, reagents, experimental methods, etc. for implementing the present invention, except for the contents specifically mentioned below, are common knowledge and common common sense in the art, and the present invention has no special restrictions. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0066] 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.

[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 tetramethylalkylthiourea reagent and the glucosidic compound of the present invention comprises the following steps:

[0069] As shown in reaction formula (a), the synthesis reaction of the present invention is carried out by adding tetramethylthiourea represented by formula (1), an alkyl halide represented by formula (2), and an organic solvent to a reaction flask A, and stirring the reaction system at 70°C under air for 16 hours. After the reaction is completed, silica gel is added and dried by spin drying, and the target product, i.e., a tetramethylalkylthiourea reagent represented by formula (3), is obtained by column chromatography. The novel tetramethylalkylthiourea 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 a sugar represented by formula (4), a tetramethylalkylthiourea 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., a 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 tetramethylalkylthiourea 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 tetramethylalkylthiourea reagent of the present invention

[0074]

[0075]

[0076] 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.

[0077] Table 2 New glucosinolate compounds of the present invention

[0078]

[0079]

[0080]

[0081] 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.

[0082] Table 3 New oxidized glucosinolate compounds of the present invention

[0083]

[0084] Example 1

[0085]

[0086] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.42 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3y (4.5 g, 95%) as a white solid. 1 H NMR (400MHz, CDCl3) δ3.42 (s, 12H), 2.70 (s, 3H). 13C NMR(101MHz, CDCl3)δ177.03,45.30,18.55.IR(neat,cm-1)3444,3001,2923,2852,1595, 1509,1465,1395,1321,1255,1206,1171,1114,1062,873,726.HRMS(ESI)m / z:[M]+Calcd for C6H15SN2147.0956,Found 147.0939.Mp:98.3-99.7℃.

[0087]

[0088] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.92 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3z (4.1 g, 91%) as a white solid. 1 H NMR (400MHz, CDCl3) δ3.41 (s, 12H), 3.14 (q, J = 7.4Hz, 2H), 1.34 (t, J = 7.4Hz, 3H). 13 C NMR(101MHz, CDCl3)δ175.75,45.34,30.22,14.81.IR(neat,cm-1)2921,2852,2860,1456,1377,754,683.HRMS(ESI)m / z:[M]+Calcd for C7H 17 SN2161.1112,Found161.1108.Mp:127.8-128.5℃.

[0089] Example 3

[0090]

[0091] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.88 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3aa (3.7 g, 86%) as a white solid. 1H NMR (400MHz, CDCl3) δ6.84(d,J=8.0Hz,2H),6.62(d,J=8.4Hz,2H),4.88(d,J=7.9Hz,1H),4.31(d,J=6.7Hz,1H),3.80(s,2 H),3.53(s,3H),3.26(s,12H),3.05(d,J=6.3Hz,2H),2.90–2.72(m,2H),2.62(s,1H),1.75(d,J=3.0Hz,4H),1.23(s,9H). 13 C NMR (101MHz, CDCl3) δ175.46,172.26,157.64,155.01,130.22,128.01,114.40,7 9.75,66.87,54.50,52.15,44.62,37.23,34.78,28.19,28.00,26.48.IR(neat,cm -1 )2920,2859,1658,1556,1245,1156,1028,796,742,693.HRMS(ESI)m / z:[M]+Calcd forC 24 H 40 SO5N3482.2683,Found 482.2681.

[0092] Example 4

[0093]

[0094] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.61 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was dried and purified by column chromatography to afford 3ab (3.2 g, 85%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.30 (m, 5H), 6.72 (d, J = 14.6Hz, 1H), 6.29 (s, 1H), 4.02 (s, 2H), 3.46 (s, 12H). 13 C NMR (101MHz, CDCl3) δ175.07,136.11,128.85,128.59,126.87,121.77,45.68,38. 98.IR(neat,cm-1)2857,1560,1438,1028,893,754,683.HRMS(ESI)m / z:[M]+Calcd for C 14 H 21SN2249.1420,Found 249.1431.Mp:78.3-79.8℃.

[0095] Example 5

[0096]

[0097] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.23 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3ac (3.9 g, 90%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.11(s,4H),3.37(s,14H),3.00(s,2H),2.29(s,3H). 13 C NMR (101MHz, CDCl3) δ175.85,136.91,134.88,129.60,128.76,45.42,37.36,35.21,21.13.IR(neat,cm -1 )1548,1436,1264,1028,901,754,738,689.HRMS(ESI)m / z:[M]+Calcd for C 14 H 23 SN2251.1576,Found 251.1559.Mp:153.2-154.4℃.

[0098] Example 6

[0099]

[0100] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.86 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3ad (3.6 g, 86%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.13(d,J=5.0Hz,1H),6.92(s,1H),6.91–6.87(m,1H),3.44(t,J=6.6Hz,2H),3.34(s,12H),3.25(t,J=6.5Hz,2H). 13C NMR (101MHz, CDCl3) δ175.64,140.33,127.37,126.51,124.64,44.79,37.19,29.99.IR(neat,cm -1 )1539,1428,1264,1028,754,738,689.HRMS(ESI)m / z:[M]+Calcd for C 11 H 19 S2N2243.0984,Found243.0982.Mp:155.3-156.2℃.

[0101] Example 7

[0102]

[0103] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.95 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was dried and purified by column chromatography to afford 3ae (3.9 g, 88%) as a white solid. 1 H NMR (400MHz, CDCl3) δ4.48(dd,J=7.9,2.5Hz,1H),4.21(d,J=2.5Hz,1H),4.12(d,J=8.0Hz,1H),3.78(dd,J=13.0,1.5Hz,1H),3.60(d,J=13.0Hz,1H ),3.54–3.45(m,2H),3.42(d,J=13.3Hz,2H),3.36(s,12H),3.05(t,J=7.1 Hz,2H),1.67(m,4H),1.42(s,3H),1.35(s,3H),1.29(s,3H),1.23(s,3H). 13 C NMR (101MHz, CDCl3) δ175.60,108.83,108.43,102.46,72.42,70.94,70.86,70.03,60. 90,53.54,50.12,44.75,34.99,28.41,26.49,26.43,25.85,25.35,23.96.IR(neat,cm -1 )1236,1156,1136,1126,1106,1028,996,796,742,693.HRMS(ESI)m / z:[M]+Calcd for C 21 H 39 SO6N2447.2523,Found447.2509.

[0104] Example 8

[0105]

[0106] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.78 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3af (3.8 g, 92%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.62(m,4H),3.68(t,J=5.7Hz,2H),3.32(s,12H),3.02(t,J=6.2Hz,2H),2.02–1.84(m,2H). 13 C NMR (101MHz, CDCl3) δ175.48,168.28,134.33,131.61,123.30,44.74,35.86,32.62,28.42.IR(neat,cm -1 )2912,2836,1548,1436,1221,1028,754,738,689.HRMS(ESI)m / z:[M]+Calcd for C 16 H 22 SO2N3320.1427,Found320.1420.Mp:139.4-141.0℃.

[0107] Example 9

[0108]

[0109] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (2.99 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3ag (2.6 g, 90%) as a white solid. 1 H NMR (400MHz, DMSO-d6) δ11.79(s,1H),7.84(d,J=8.1Hz,1H),7.49(t,J=7.6Hz,1H),7.35(d ,J=8.4Hz,1H),7.20(t,J=7.6Hz,1H),6.58(s,1H),4.51(s,2H),3.14(s,12H),3.09(s,2H). 13C NMR(101MHz,DMSO-d6)δ172.82,161.63,145.80,139.71,131.42,125.28,122.86,122.50,117.46,116.48,49.03,44.05,34.70.IR(neat,cm -1 )2836,1714,1548,1436,1229,754,738,689.HRMS(ESI)m / z:[M]+Calcd for C 15 H 22 SON3292.1478,Found 292.1476.Mp:107.9-108.8℃.

[0110] Example 10

[0111]

[0112] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (2.15 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3ah (2.2 g, 98%) as a white solid. 1 H NMR (400MHz, CDCl3) δ3.37(s,12H),3.05(d,J=7.7Hz,1H),2.51–2.39(m,2H),2.06(d,J=6.8Hz,2H),1.87–1.58(m,4H). 13 C NMR (101MHz, CDCl3) δ175.50,44.84,40.95,35.00,34.04,27.59,24.58,17.73.IR(neat,cm -1 )1436,1229,1028,881,754,738,689.HRMS(ESI)m / z:[M]+Calcd for C 10 H 21 SN2201.1420,Found 201.1423.Mp:79.3-80.2℃.

[0113] Example 11

[0114]

[0115] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (4.09 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3ai (4.1 g, 95%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.34–7.18(m,5H),3.46(t,J=7.0Hz,2H),3.34(s,12H),3.04(t,J=7.0Hz,2H). 13 C NMR (101MHz, CDCl3) δ175.75,138.01,128.90,128.79,127.24,44.75,36.78,35.40.IR(neat,cm -1 )1548,1436,1264,1028,901,754,732,683.HRMS(ESI)m / z:[M]+Calcd for C 13 H 21 SN2237.1420,Found 237.1423.Mp:144.8-145.7℃.

[0116] Example 12

[0117]

[0118] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (4.11 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3aj (3.8 g, 91%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.30 (m, 5H), 6.72 (d, J = 14.6Hz, 1H), 6.29 (s, 1H), 4.02 (s, 2H), 3.46 (s, 12H). 13 C NMR (101MHz, CDCl3) δ175.07,136.11,128.85,128.59,126.87,121.77,45.68,38. 98.IR(neat,cm-1)2857,1560,1438,1028,893,754,683.HRMS(ESI)m / z:[M]+Calcd for C 14 H 21 SN2249.1420,Found 249.1431.Mp:78.3-79.8℃.

[0119] Example 13

[0120]

[0121] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (4.54 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was dried and column chromatography was performed to obtain 3ak (4.41 g, 88%) as a white solid. 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). 13 C NMR (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,Found 251.1582.

[0122] Example 14

[0123]

[0124] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (4.05 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3al (3.82 g, 85%) as a white solid. 1H NMR (400MHz, CDCl3) δ7.15(d,J=8.6Hz,1H),6.65(d,J=8.6Hz,1H),6.60(s,1H),4.04(t,J=5.4Hz,2H),3.44(s,12H),3. 33(t,J=7.0Hz,2H),2.90–2.81(m,2H),2.46(m,1H),2.34(d,J=9.7Hz,1H),2.06(m,9H),1.65–1.29(m,6H),0.87(s,3H). 13 CNMR(101MHz, CDCl3)δ175.83,156.32,138.01,132.61,126.47,114.42,112.10,65.66,50.38,47.9 9,44.91,43.95,38.31,35.87,32.31,31.56,29.64,29.51,26.49,25.91,21.57,13.87.IR(neat,cm -1 )2919,2849,1632,1556,1236,1156,1028,996,796,742,693.HRMS(ESI)m / z:[M]+Calcd for C 27 H 41 SO2N2457.2883,Found 457.2876.Mp:177.7-178.5℃.

[0125] Example 15

[0126]

[0127] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (4.05 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3am (3.82 g, 85%) as a white 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). 13C 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 forC 21 H 23 SO3N2383.1424,Found 383.1409.Mp:204.3-205.1℃.

[0128] Example 16

[0129]

[0130] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (4.49 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3an (4.21 g, 90%) as a white solid. 1 H NMR (400MHz, CDCl3) δ5.37(d,J=4.7Hz,1H),3.49(s,12H),3.14(dd,J=19.4,9.8Hz,2H),3.06(s,1H),2.40(d,J=12.4Hz,1H),2.19(d,J=12. 1Hz,1H),2.03–1.91(m,3H),1.80(m,4H),1.57–1.03(m,27H),0.98(s,3H),0.88(d,J=6.5Hz,3H),0.83(dd,J=6.6,1.7Hz,6H),0.64(s,3H). 13 C NMR (101MHz, CDCl3) δ173.88,139.37,123.65,56.60,56.08,50.53,49.96,49.50,45.08,44.92,42.27,39.58,39.49,39.24, 36.58,36.15,35.74,31.75,31.66,30.07,28.16,27.98,24.22,23.79,22.79,22.53,20.82,19.20,18.69,11.83.IR(neat,cm -1)1554,1438,1221,1156,1136,1108,1028,996,885,796,742,693.HRMS(ESI)m / z:[M]+Calcd for C 32 H 57 SN2501.4237,Found 501.4233.

[0131] Example 17

[0132]

[0133] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (3.83 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography was performed to obtain 3ao (3.42 g, 82%) as a white solid. 1 H NMR (501MHz, CDCl3) δ5.47(t,J=9.8Hz,1H),4.98(t,J=9.6Hz,1H),4.89(d,J=3.5Hz,1H),4.81(dd,J=10.3,3.5Hz,1H),4.24–4.13(m ,1H),3.69(dd,J=13.6,3.3Hz,1H),3.45(s,12H),3.42(s,3H),3.25(dd,J=13.6,4.5Hz,1H),2.14(s,3H),2.04(s,3H),1.97(s,3H). 13 C NMR (126MHz, CDCl3) δ176.47,171.07,170.26,169.59,96.98,70.69,70.21,69.21,67.37,56.22,44.73,37.14,21.38,20.70,20.62.IR(neat,cm -1 )3360,3259,2360,1221,1162,1123,1106,1028,796,742,693.HRMS(ESI)m / z:[M]+Calcd forC 18 H 31 SO8N2435.1796,Found 435.1791.

[0134] Example 18

[0135]

[0136] Tetramethylthiourea (1.32 g, 10 mmol, 1 equiv), alkyl bromide (2.45 g, 10 mmol, 1 equiv), and ethanol (10 mL) were added to a reaction tube and reacted at 70°C for 16 hours. After the reaction was complete, the mixture was dried and purified by column chromatography to afford 3ap (2.18 g, 93%) as a white solid. 1 H NMR (501MHz, CDCl3) δ6.91(d,J=1.2Hz,1H),6.81–6.76(m,2H),3.89(s,3H),3.83(s,3H),3.49(t,J=7.2Hz,2H),3.38(s,12H),3.00(t,J=7.2Hz,2H). 13 C NMR (126MHz, CDCl3) δ175.98,149.28,148.18,130.66,120.78,112.26,111.38,56.40,55.99,44.75,37.06,34.98.IR(neat,cm -1 )1583,1462,1221,1148,1126,1106,1028,996,796,742,693.HRMS(ESI)m / z:[M]+Calcd for C 15 H 25 SO2N2297.1631,Found 297.1630.

[0137] Example 19

[0138]

[0139] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (198.8 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). The mixture was reacted at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5a as a white solid (133.6 mg, 99%). 1 H NMR (400MHz, CDCl3) δ7.46–7.29(m,18H),7.23(m,2H),7.19–7.11(m,4H),5.05–4.85(m,4H),4.87–4.72(m,1H) ,4.64(q,J=12.2Hz,3H),4.53(d,J=9.6Hz,1H),3.89–3.64(m,4H),3.53(m,2H),3.11–2.90(m,4H),2.38(s,3H). 13C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,138.1,137.5,135.9,129.2,128.6,128.5,128.4,128.0,127. 9,127.8,127.7,86.7,85.3,81.9,79.2,78.1,75.8,75.6,75.1,73.6,69.2,36.2,32.5,21.1.IR(neat,cm -1 )2900,2862,2360,1508,1452,1355,1276,1261,1132,1083,1056,1028,989,763,750,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 43 H 46 O5SNa697.2964,Found 697.2947.Mp:52.1–53.4℃.

[0140] Example 20

[0141]

[0142] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (190.4 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). The mixture was reacted at 25°C for 16 hours. After completion, the mixture was spin-dried and purified by column chromatography to afford 5b as a white solid (118.9 mg, 90%). 1 H NMR (400MHz, CDCl3) δ7.36–7.20(m,20H),7.20–7.13(m,5H),4.94–4.76(m,4H),4.72(m,1H),4 .61–4.50(m,3H),4.48–4.40(m,1H),3.87–3.55(m,5H),3.51–3.37(m,2H),3.08–2.82(m,4H). 13 C NMR (101MHz, CDCl3) δ140.6,138.6,138.3,138.2,138.1,128.7,128.6,128.5,128.4,128.1,127.9,12 7.8,127.7,126.4,86.7,85.3,81.9,79.2,78.1,75.8,75.6,75.1,73.6,69.3,36.7,32.3.IR(neat,cm -1)2866,1496,1454,1361,1122,1089,1056,1026,908,744,719,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 44 O5SNa 683.2807,Found 683.2810.Mp:52.1–53.3℃.

[0143] Example 21

[0144]

[0145] To a reaction tube, sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (194.0 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 dried and column chromatography afforded 5c (129.4 mg, 97%) as a yellow solid. 1 H NMR (400MHz, CDCl3) δ7.36–7.20(m,18H),7.17–7.12(m,2H),7.09–7.06(m,1H),6.86(m,1H),6.81–6.75(m,1H),4.85(m,4H),4. 71(d,J=10.2Hz,1H),4.60–4.50(m,3H),4.43(d,J=9.7Hz,1H),3.80–3.54(m,4H),3.49–3.35(m,2H),3.17(m,2H),2.99(m,2H). 13 C NMR (101MHz, CDCl3) δ143.1,138.6,138.3,138.2,138.1,128.6,128.5,128.1,128.0,127.9,127.8,127.7 ,127.0,125.2,123.7,86.8,85.4,81.9,79.3,78.1,75.9,75.6,75.2,73.6,69.2,32.7,31.1.IR(neat,cm -1 )2902,2862,2360,1496,1452,1359,1274,1209,1064,1028,908,846,821,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 40 H 42O5S2Na 689.2371,Found 689.2359.Mp:69.2–70.5℃.

[0146] Example 22

[0147]

[0148] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (240.0 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). The mixture was reacted at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography was performed to obtain 5d (132.4 mg, 89%) as a colorless oil. 1 H NMR (400MHz, CDCl3) δ7.82–7.75(m,2H),7.64(m,2H),7.38–7.32(m,2H),7.25(m,16H),7.17–7.12(m,2H),4.93–4.76(m,4H),4.7 1(d,J=10.2Hz,1H),4.56(m,2H),4.52–4.43(m,2H),3.76(m,2H),3.70–3.57(m,4H),3.48–3.39(m,2H),2.75(m,2H),2.03(m,2H). 13 C NMR (101MHz, CDCl3) δ168.3,138.6,138.3,138.2,138.0,133.9,132.2,128.5,128.4,128.0,127.9,127.8,127. 7,127.6,123.3,86.7,85.4,81.8,79.1,78.0,77.4,75.8,75.5,75.1,73.4,69.1,37.2,29.3,28.4.IR(neat,cm -1 )2895,2858,2360,1768,1703,1454,1394,1357,1134,1083,1055,1028,889,748,717,692,528.HRMS(ESI)m / z:[M+Na] + Calcd for C 45 H 45 NO7SNa 766.2814,Found766.2800.

[0149] Example 23

[0150]

[0151] To a reaction tube, sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (181.3 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 dried and column chromatography afforded 5e (86.2 mg, 72%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.44–7.27(m,20H),7.21(d,J=6.9Hz,2H),4.99–4.92(m,2H),4.91–4.82(m,2H),4.75(d ,J=10.4Hz,1H),4.67–4.54(m,4H),3.82–3.58(m,4H),3.54–3.42(m,2H),3.28(m,1H),1.39(t,J=7.2Hz,6H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.1,128.5,128.4,128.0,127.8,127.7,127.6 ,86.8,84.7,82.1,79.1,78.1,75.8,75.6,75.1,73.5,69.3,35.6,24.1.IR(neat,cm -1 )2902,2868,2360,1716,1454,1361,1263,1153,1120,1070,1028,908,732,692.Mp:93.2–94.8℃.

[0152] Example 24

[0153]

[0154] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (168.8 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 is dried and purified by column chromatography to afford 5f (67.0 mg, 56%) as a white solid. 1H NMR (400MHz, CDCl3) δ7.40–7.22(m,18H),7.20–7.12(m,2H),4.92(m,2H),4.82(m,2H),4.75–4.67(m,1H),4.57(t,J= 7.0Hz,2H),4.49(d,J=9.8Hz,1H),3.84–3.55(m,5H),3.50–3.30(m,3H),2.04(m,2H),1.81–1.70(m,2H),1.60(m,4H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,128.5,128.4,128.0,127.8,127.7,127.6,86.8,8 5.5,82.1,79.1,78.1,75.8,75.5,75.1,73.5,69.4,43.9,34.4,34.2,24.8,24.6.IR(neat,cm -1 )2904,2868,1496,1454,1361,1139,1087,1056,1026,995,752,731,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 39 H 44 O5SNa 647.2807,Found647.2792.Mp:52.9–53.8℃.

[0155] Example 25

[0156]

[0157] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (176.0 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 product was spin-dried and purified by column chromatography to yield 5 g (77.7 mg, 61%) of a white solid. 1H NMR (400MHz, CDCl3) δ7.39–7.34(m,2H),7.33–7.21(m,16H),7.19–7.14(m,2H),5.85–5.70(m,2H),4.92(m,2H),4.86–4.77( m,2H),4.71(dt,J=8.6,4.8Hz,1H),4.60–4.50(m,3H),3.77–3.54(m,5H),3.49–3.37(m,2H),2.11–1.65(m,6H),1.59(m,1H). 13 C NMR (101MHz, CDCl3) δ138.7,138.4,138.3,138.2,130.5,129.9,128.5,128.4,128.0,127.9,127.8,127.7,127.6,86.9,86.2,84 .7,82.2,82.0,79.2,79.1,78.1,75.8,75.7,75.6,75.1,73.5,69.3,42.1,40.6,30.8,30.0,25.0,24.9,19.8,19.6.IR(neat,cm -1 )2904,1489,1456,1361,1274,1138,1087,1055,1026,871,750,734,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 40 H 44 O5SNa 659.2807,Found659.2785.Mp:86.9–88.2℃.

[0158] Example 26

[0159]

[0160] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (196.4 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, spin dry the product and column chromatography yields 5h (95.3 mg, 71%) as a white solid. 1H NMR (400MHz, CDCl3) δ7.40–7.24(m,18H),7.22–7.13(m,2H),4.97–4.79(m,4H),4.73(m,2H),4.64–4.44(m,4H ),4.24–3.98(m,2H),3.86–3.56(m,5H),3.46(d,J=8.7Hz,1H),1.60(d,J=13.3Hz,6H),1.19(t,J=7.1Hz,3H). 13 C NMR (101MHz, CDCl3) δ173.9,138.6,138.2,128.4,128.3,128.1,127.9,127.8,127.7,127.6,86. 9,84.0,81.3,78.8,77.8,75.8,75.4,75.0,73.4,69.1,61.3,48.1,26.5,26.1,14.1.IR(neat,cm -1 )2902,2868,1718,1454,1361,1263,1153,1120,1066,1028,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 40 H 46 O7SNa 693.2862,Found 693.2857.Mp:66.9–67.8℃.

[0161] Example 27

[0162]

[0163] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (284.6 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 5i (160.7 mg, 95%) as a colorless liquid. 1H NMR (400MHz, CDCl3) δ7.39–7.21(m,23H),7.16(d,J=7.3Hz,2H),5.21–5.00(m,2H),4.95–4.70(m,5H),4.61–4.41(m,4H),4.37– 4.17(m,2H),4.13–4.03(m,1H),3.75–3.54(m,5H),3.53–3.38(m,3H),2.73–2.48(m,2H),2.24–2.08(m,1H),2.06–1.75(m,5H). 13 C NMR (101MHz, CDCl3) δ172.7,172.6,165.7,154.8,154.3,138.5,138.2,138.1, 138.0,137.9,136.8,136.6,128.5,128.4,128.3,128.0,127.9,127.8,127.7,8 6.6,85.6,85.5,81.7,79.0,77.9,75.8,75.5,75.1,73.4,69.1,67.0,63.6,59. 3,58.9,47.0,46.5,31.0,30.0,29.4,29.1,27.6,27.4,24.4,23.5.IR(neat,cm -1 )2868,1743,1701,1645,1496,1454,1373,1355,1138,1118,1085,1062,1028,914,748,692.HRMS(ESI)m / z:[M+H] + Calcd for C 50 H 56 NO9S 846.3676,Found 846.3654.

[0164] Example 28

[0165]

[0166] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (296.0 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 spin-dried and column chromatography afforded 5j (141.9 mg, 82%) as a colorless liquid. 1H NMR (400MHz, CDCl3) δ8.00(d,J=2.2Hz,1H),7.76(d,J=7.7Hz,1H),7.39(dt,J=7.3,3 .7Hz,1H),7.34–7.22(m,4H),7.22–7.11(m,17H),7.08–6.99(m,2H),6.90(d,J=8.4H z,1H),5.11(s,1H),4.99(s,1H),4.84–4.52(m,5H),4.50–4.30(m,4H),4.09(t,J=6. 2Hz,2H),3.65–3.44(m,6H),3.40–3.27(m,2H),2.77–2.31(m,2H),1.93–1.74(m,2H). 13 C NMR (101MHz, CDCl3) δ190.8,171.4,160.5,140.5,138.6,138.2,138.1,138 .0,136.4,135.6,132.8,132.5,129.6,129.3,128.5,128.4,128.2,128.1, 128.0,127.9,127.8,127.7,125.2,121.2,86.7,85.6,81.8,79.1,77.9,75 .8,75.6,75.1,73.7,73.5,69.1,63.6,53.6,40.3,29.3,27.7.IR(neat,cm -1 )2868,1732,1647,1489,1413,1300,1276,1259,1138.1120,1068,1026,748,732,692,642.HRMS(ESI)m / z:[M+Na] + Calcd for C 53 H 52 O9SNa 887.3230,Found 887.3220.

[0167] Example 29

[0168]

[0169] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (316.5 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 was evaporated to dryness and column chromatography afforded 5k (157.7 mg, 89%) as a colorless liquid. 1H NMR (400MHz, CDCl3) δ7.38–7.22(m,18H),7.16(m,2H),4.83(m,5H),4.63–4.50(m,4H),4.40(m,2H),4.21(d,J=7.9Hz,1H),3. 90(dd,J=13.0,1.7Hz,1H),3.76–3.38(m,11H),2.74(m,2H),1.70(m,4H),1.52(s,3H),1.46(s,3H),1.40(s,3H),1.32(s,3H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.1,128.5,128.4,128.3,128.0,127.9,127.8,127.6,108.9,108.5,102.7,86.7,85.3,81 .9,79.1,78.0,75.8,75.5,75.1,73.5,72.2,71.4,71.1,70.3,70.0,69.1,61.1,30.8,28.8,26.6,26.0,25.5,24.1.IR(neat,cm -1 )2902,2866,1456,1373,1251,1205,1163,1114,1039,1028,908,889,748,731,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 50 H 62 O 11 SNa 893.3911,Found 893.3874.

[0170] Example 30

[0171]

[0172] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (349.1 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 51 (116.6 mg, 62%) as a yellow solid. 11H NMR (400 MHz, CDCl3) δ 7.27 (m, 2H), 7.24–7.13 (m, 16H), 7.08 (m, 2H), 5.20 (d, J = 5.1 Hz, 1H), 4.82 (dd, J = 10.5, 8.9 Hz, 2H), 4.73 (dd, J = 11.0, 5.8 Hz, 2H), 4.62 (d, J = 10.4 Hz, 1H), 4.51–4.42 (m, 3H), 3.65 (dd, J = 10.8, 1.7 Hz, 1H), 3.57 (m, 2H), 3.48 (t, J = 9.3 Hz, 1H), 3.40–3.29 (m, 2H), 2.82–2.71 (m, 1H), 2.30 (d, J = 6.1 Hz, 2H), 1.96–1.68 (m, 5H), 1.60–1.12 (m, 14H), 1.06 (m, 7H), 0.89 (s, 4H), 0.82 (d, J = 6.5 Hz, 4H), 0.77 (dd, J = 6.6, 1.7 Hz, 6H), 0.58 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 141.8, 138.6, 138.3, 138.1, 128.4, 128.3, 128.0, 127.8, 127.7, 127.5, 121.1, 86.8, 84.5, 82.0, 79.1, 78.1, 75.8, 75.5, 75.0, 73.4, 69.4, 56.8, 56.2, 50.3, 44.9, 42.4, 40.6, 39.8, 39.8, 39.6, 36.8, 36.2, 35.8, 31.9, 30.5, 28.3, 28.0, 24.3, 23.9, 22.9, 22.6, 20.9, 19.4, 18.8, 11.9. IR (neat, cm -1 ) 2922, 1752, 1655, 1453, 1406, 1381, 1333, 1249, 1157, 1028, 908, 748, 732, 694, 523. HRMS (ESI) m / z: [M+Na] + Calcd for C 61 H 80 O5SNa 947.5624, Found 947.5629. Mp: 80.5–81.6 °C.

[0173] Example 31

[0174]

[0175] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (111.9 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 product was spin-dried and purified by column chromatography to afford 5m (116.6 mg, 98%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.38–7.33(m,2H),7.32–7.21(m,16H),7.18–7.13(m,2H),4.93–4.71(m,5 H),4.56(q,J=12.3Hz,3H),4.35(d,J=9.7Hz,1H),3.68(m,4H),3.50–3.40(m,2H),2.22(s,3H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,138.1,128.5,128.4,128.0,127.9,127.8 ,127.7,86.7,85.4,81.3,79.3,78.1,75.8,75.5,75.1,73.6,69.1,13.0.IR(neat,cm -1 )2906,2868,1496,1452,1363,1130,1085,1066,1055,1028,948,887,756,732,692.NMR was consistent with the literature. 11 Mp:52.3–53.5℃.

[0176] Example 32

[0177]

[0178] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (172.9 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 yielded 5n (107.6 mg, 92%) as a white solid. 1H NMR (400MHz, CDCl3) δ7.43(m,2H),7.41–7.29(m,16H),7.26–7.20(m,2H),4.98(d,J=10.9Hz,2H),4.94–4.85(m,2H),4.80(d,J=10 .2Hz,1H),4.63(q,J=12.2Hz,3H),4.53(d,J=9.7Hz,1H),3.85–3.63(m,4H),3.52(m,2H),2.96–2.70(m,2H),1.39(t,J=7.4Hz,3H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,138.1,128.5,128.4,128.0,127.9,127.8,127.7 ,127.6,86.8,85.1,81.9,79.2,78.1,75.8,75.5,75.1,73.5,69.2,25.0,15.3.IR(neat,cm -1 )2902,2868,1716,1683,1558,1456,1363,1066,1055,1026,950,750,732,692.NMR was consistent with the literature. 12 Mp:69.7–71.2℃.

[0179] Example 33

[0180]

[0181] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (161.5 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 was dried and purified by column chromatography to afford 5o (95.6 mg, 78%) as a white solid. 1H NMR (400MHz, CDCl3) δ7.38–7.34(m,2H),7.33–7.22(m,16H),7.18–7.12(m,2H),4.91(m,2H),4.86–4.77(m,2H),4.73(d,J=10.3Hz,1 H),4.55(m,3H),4.43(d,J=9.7Hz,1H),3.67(m,4H),3.44(m,2H),2.73(m,2H),1.70–1.54(m,2H),1.39(m,2H),0.89(t,J=7.4Hz,3H). 13 C NMR (101MHz, CDCl3) δ138.7,138.3,138.2,138.1,128.5,128.4,128.0,127.9,127.8,127.7,127. 6,86.8,85.4,82.0,79.2,78.1,75.8,75.6,75.1,73.5,69.2,32.1,30.6,22.1,13.8.IR(neat,cm -1 )2862,2360,1496,1454,1359,1274,1209,1062,1028,908,732,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 38 H 44 O5SNa635.2807,Found 635.2800.Mp:46.7–47.2℃.

[0182] Example 34

[0183]

[0184] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (178.4 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 (92.3 mg, 72%) as a white solid. 1H NMR(400MHz, CDCl3)δ7.43(m,2H),7.40–7.29(m,16H),7.23(m,2H),4.98(d d,J=10.6,4.3Hz,2H),4.93–4.85(m,2H),4.80(d,J=10.2Hz,1H),4.63(m,3H ),4.50(d,J=9.7Hz,1H),3.74(m,4H),3.51(m,2H),2.89–2.68(m,2H),1.71 (m,2H),1.51–1.42(m,2H),1.40–1.29(m,4H),1.01–0.85(t,J=6.92Hz,3H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,138.1,128.5,128.4,128.0,127.9,127.8,127.7,127.6,86. 8,85.3,81.9,79.2,78.1,75.8,75.5,75.1,73.5,69.2,31.5,31.0,30.0,28.7,22.6,14.1.IR(neat,cm -1 )2926,2856,2360,1496,1454,1359,1274,1261,1062,1028,908,763,750,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 40 H 48 O5SNa 663.3120,Found663.3106.Mp:34.7–35.3℃.

[0185] Example 35

[0186]

[0187] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (160.3 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 5q (117.3 mg, 96%) as a colorless liquid. 1H NMR (400MHz, CDCl3) δ7.38–7.20(m,18H),7.16(m,2H),4.85(m,6H),4.75–4.64(m,1H) ),4.63–4.36(m,4H),3.86–3.57(m,5H),3.56–3.36(m,2H),3.18(m,1H),1.83(s,3H). 13 C NMR (101MHz, CDCl3) δ140.8,138.7,138.3,138.2,138.1,128.5,128.4,128.0,127.9,127.8,127.7 ,127.6,114.3,86.9,83.3,81.7,79.1,78.1,75.8,75.5,75.1,73.5,69.2,37.8,20.9.IR(neat,cm -1 )2862,1496,1454,1359,1274,1209,1064,1028,904,748,732,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 38 H 42 O5SNa 633.2651,Found 633.2633.

[0188] Example 36

[0189]

[0190] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (151.9 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 5r (102.6 mg, 86%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.38–7.20(m,18H),7.18–7.11(m,2H),5.85(m,1H),5.19–5.02(m,2H),4 .98–4.65(m,5H),4.64–4.38(m,4H),3.93–3.55(m,5H),3.53–3.39(m,2H),3.30–3.12(m,1H). 13C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,138.1,133.9,128.5,128.4,128.0,127.9,127.8 ,127.7,117.7,86.9,83.3,81.7,79.0,78.2,75.8,75.5,75.1,73.5,69.2,33.3.IR(neat,cm -1 )2910,2866,1496,1452,1361,1120,1085,1055,1026,987,948,742,732,692.HRMS(ESI)m / z:[M+Na] + Calcdfor C 37 H 40 O5SNa 619.2494,Found 619.2480.Mp:38.9–39.7℃.

[0191] Example 37

[0192]

[0193] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (160.3 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 mixture is spin-dried and purified by column chromatography to afford 5s as a white solid (120.9 mg, 99%). 1 H NMR (400MHz, CDCl3) δ7.37–7.33(m,2H),7.33–7.20(m,16H),7.18–7.10(m,2H),5.82(m,1H),5.18–4.98(m,2H),4.90(d,J=10 .8Hz,1H),4.85–4.77(m,1H),4.72(m,1H),4.61–4.39(m,3H),3.77–3.53(m,4H),3.44(m,1H),2.88–2.67(m,1H),2.38(m,2H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,138.1,136.8,128.5,128.4,128.1,127.9,127.9,127.8 ,127.7,116.2,86.8,85.4,81.9,79.2,78.1,75.8,75.6,75.1,73.6,69.2,34.4,30.3.IR(neat,cm-1 )3030,2902,2862,1496,1454,1359,1276,1209,1062,1028,956,910,731,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 38 H 42 O5SNa 633.2651,Found 633.2628.Mp:36.9–37.2℃.

[0194] Example 38

[0195]

[0196] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (159.1 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 5t (112.0 mg, 92%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.38–7.21(m,18H),7.18–7.10(m,2H),4.97–4.75(m,4H),4.71(m,1H),4.66–4.52(m,3H), 4.51–4.45(m,1H),3.86–3.55(m,4H),3.49–3.38(m,2H),2.99–2.73(m,2H),2.56(m,2H),2.00(t,J=2.6Hz,1H). 13 C NMR (101MHz, CDCl3) δ138.6,138.2,138.1,138.0,128.5,128.4,128.1,128.0,127.9,127.8,127. 7,86.7,85.5,82.8,81.8,79.2,78.0,75.8,75.6,75.1,73.6,69.6,69.2,30.1,20.8.IR(neat,cm -1 )3242,2866,2360,1496,1454,1359,1274,1080,1064,1028,744,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 38 H 40 O5SNa 631.2494,Found631.2496.Mp:85.6–87.2℃.

[0197] Example 39

[0198]

[0199] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (194.0 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 the reaction is complete, spin dry the product and column chromatography yields 5u (109.4 mg, 82%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.35–7.15(m,18H),7.11(m,2H),4.94–4.64(m,5H),4.52(m,5H),3.61(m,5H),3.39(m,2H),0.10(s,9H). 13 C NMR (101MHz, CDCl3) δ138.6,138.2,138.1,138.0,128.4,128.3,128.0,127.8,127.7,127.6,1 01.6,88.3,86.7,83.2,81.4,79.2,77.9,75.7,75.3,75.1,73.4,68.9,18.4,0.0.IR(neat,cm -1 )2899,2864,1496,1454,1359,1249,1066,1026,908,840,732,683,638.HRMS(ESI)m / z:[M+Na] + Calcd for C 40 H 46 O5SSiNa 689.2733,Found 689.2714.

[0200] Example 40

[0201]

[0202] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (168.8 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 is dried and purified by column chromatography to afford 5v (86.2 mg, 69%) as a white solid. 1H NMR (400MHz, CDCl3) δ7.39–7.21(m,18H),7.15(m,2H),4.96–4.88(m,2H),4.85–4.77(m,2H),4.72(m,1H),4.65–4.37 (m,4H),3.68(m,4H),3.50–3.35(m,2H),2.80(m,1H),2.56(m,1H),2.18–2.00(m,2H),1.90–1.64(m,4H),1.58(s,1H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.1,128.5,128.4,128.0,127.9,127.8,127.7,127.6,86. 7,85.1,82.0,79.1,78.0,75.8,75.5,75.1,73.5,69.2,37.3,35.7,28.1,28.0,18.0.IR(neat,cm -1 )2900,2866,2360,1496,1454,1361,1274,1139,1087,1058,1026,750,736,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 39 H 44 O5SNa 647.2807,Found 647.2787.Mp:43.6–44.1℃.

[0203] Example 41

[0204]

[0205] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (182.0 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 5w (115.1 mg, 89%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.46–7.19(m,25H),5.03–4.80(m,4H),4.78–4.46(m,4H),4.30(d,9.8Hz,1H),4.08(d,J=13.1Hz,1H),3.98–3.40(m,7H). 13C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,138.0,137.8,129.3,128.6,128.5,128.4,128.0,127.9 ,127.8,127.7,127.2,86.7,83.3,81.8,79.1,78.1,75.8,75.4,75.1,73.6,69.2,34.4.IR(neat,cm -1 )2866,2360,1496,1454,1361,1064,1028,910,732,683.Mp:59.6–60.3℃.

[0206] Example 42

[0207]

[0208] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (184.4 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 dried and purified by column chromatography to afford 5x (72.9 mg, 56%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.40–7.23(m,18H),7.20–7.15(m,2H),5.65(s,2H),4.92(m,2H),4.87–4.79(m,2H),4.74(d,J=10.2Hz,1H),4.57(q,J =12.0Hz,3H),4.42(d,J=9.7Hz,1H),3.68(m,4H),3.51–3.34(m,2H),2.72(m,2H),2.31–2.18(m,1H),2.08–1.73(m,5H),1.40–1.25(m,1H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.1,128.5,128.4,128.0,127.9,127.8,127.7,127.6,126.0,86.7,85.7,85. 6,82.0,79.2,78.0,75.8,75.6,75.1,73.5,69.2,37.4,37.2,34.0,31.4,31.2,28.2,28.1,24.9,24.8.IR(neat,cm -1)2906,2868,1496,1454,1361,1139,1089,1056,1026,752,734,683.HRMS(ESI)m / z:[M+Na] + Calcd for C 41 H 46 O5SNa 673.2964,Found 673.2948.Mp:63.4–65.1℃.

[0209] Example 43

[0210]

[0211] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (223.4 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 reacted at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5y (72.9 mg, 50%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ11.99 (s, 1H), 7.81 (d, J = 8.1Hz, 1H), 7.45 (t, J = 7.3Hz, 1H) ,7.38(t,J=9.5Hz,1H),7.32–6.97(m,20H),6.67(s,1H),4.85–4.65(m,4H),4.63 –4.53(m,2H),4.53–4.34(m,4H),4.12(d,J=13.6Hz,1H),3.98(d,J=13.4Hz,1H), 3.83–3.72(m,1H),3.64(m,2H),3.56(d,J=7.5Hz,2H),3.40(m,2H),1.84(s,2H). 13 C NMR (126MHz, CDCl3) δ163.6,148.5,138.7,138.4,138.1,138.0,137.6,130.9,128.5,128.4,128.3,128.2,128.0,127.9,12 7.8,127.7,124.8,122.9,119.0,117.0,86.6,83.5,81.5,79.0,77.8,75.8,75.5,75.1,73.6,69.0,30.9,29.7.IR(neat,cm -1)2902,2868,2360,1654,1508,1064,1028,750,692,669.HRMS(ESI)m / z:[M+Na] + Calcd for C 44 H 45 O6NSNa 738.2865,Found 738.2861.

[0212] Example 44

[0213]

[0214] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (180.8 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 mixture was spin-dried and column chromatography yielded 5z (127.7 mg, 99%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.39–7.21(m,18H),7.15(m,2H),4.96–4.64(m,5H),4.55(m,3H),4.43(d,J=9.8 Hz,1H),3.77–3.53(m,4H),3.44(m,2H),2.82(m,2H),2.57(t,J=7.1Hz,2H),2.04(s,3H),1.91(m,2H). 13 C NMR (101MHz, CDCl3) δ138.6,138.4,128.6,127.9,86.7,85.5,81.8,79.2,78.0,75.8,75.6,75.1,73.5,69.2,33.0,29.8,29.3,15.5.IR(neat,cm -1 )2912,2862,1496,1454,1361,1274,1261,1064,1028,908,748,732,694.HRMS(ESI)m / z:[M+H] + Calcd for C 38 H 45 O5S2645.2708, Found 645.2689.

[0215] Example 45

[0216]

[0217] To a reaction tube, sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (168.1 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 the reaction was complete, the mixture was spin-dried and column chromatography afforded 5aa (79.8 mg, 64%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.37–7.21(m,18H),7.16(m,2H),4.95–4.66(m,5H),4.51(m,4H),3 .83–3.54(m,4H),3.49–3.37(m,2H),2.92–2.69(m,2H),2.44(m,2H),2.06–1.92(m,2H). 13 C NMR (101MHz, CDCl3) δ138.5,138.1,138.0,137.9,128.5,128.3,128.0,127.9,127.8,119.4,8 6.6,85.7,81.6,79.0,77.9,75.8,75.6,75.1,73.5,69.1,36.3,30.0,26.1,15.8.IR(neat,cm -1 )2916,2864,1496,1459,1359,1274,1261,1209,1124,1064,1028,995,734,683.HRMS(ESI)m / z:[M+H] + Calcdfor C 38 H 42 NO5S 624.2784,Found 624.2762.

[0218] Example 46

[0219]

[0220] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (190.4 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 was dried and column chromatography afforded 5ab (79.8 mg, 47%) as a colorless liquid. 1H NMR(400MHz, CDCl3)δ7.42–7.10(m,25H),4.88(d,J=10.9Hz,1H),4.77–4.59(m,4H),4 .53(m,4H),4.13(m,1H),4.02(t,J=9.8Hz,1H),3.86–3.68(m,4H),2.96–2.73(m,4H). 13 C NMR (101MHz, CDCl3) δ140.3,138.5,138.4,138.3,138.1,128.6,128.5,128.4,128.3,128.0,127.9,127.8,12 7.7,127.6,127.5,126.4,82.4,80.4,77.3,76.4,75.1,73.4,72.2,72.1,72.0,69.2,36.4,32.6.IR(neat,cm -1 )2868,1496,1454,1363,1207,1155,1089,1026,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 44 O5SNa 683.2807,Found 683.2783.

[0221] Example 47

[0222]

[0223] To a reaction tube, sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (190.4 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 dried and column chromatography afforded 5ac (52.9 mg, 40%) as a white solid. 1 H NMR (400MHz, CDCl3) δ7.38–7.10(m,25H),4.94(d,J=11.6Hz,1H),4.79(dd,J=23.9,10.2Hz,2H),4.70(s,2H),4.60(d, J=11.6Hz,1H),4.46–4.36(m,3H),3.93(d,J=2.6Hz,1H),3.84(t,J=9.4Hz,1H),3.64–3.48(m,4H),3.02–2.83(m,4H). 13C NMR (101MHz, CDCl3) δ139.6,137.7,137.3,137.2,136.8,127.5,127.4,127.3,127.2,127.0,126.8,126.7 ,126.6,126.5,125.2,84.2,83.0,77.3,76.2,74.7,73.5,72.6,72.5,71.7,67.8,35.7,30.8.IR(neat,cm -1 )2962,1558,1541,1456,1361,1257,1055,1028,1016,908,867,788,731,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 42 H 44 O5SNa683.2807,Found 683.2803.Mp:56.2–57.3℃.

[0224] Example 48

[0225]

[0226] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (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 evaporated to dryness and column chromatography afforded 5ad (152.3 mg, 85%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.27(d,J=7.1Hz,2H),7.17(m,23H),7.11–6.93(m,5H),5.21(d,J=8.1Hz,1H),5.09(s,1H),4.98(d,J=6.0Hz,2H),4.87– 4.63(m,5H),4.51–4.29(m,4H),4.12–4.01(m,2H),3.65–3.46(m,4H), 3.35(m,2H),2.97(m,2H),2.56(m,2H),1.88–1.72(m,2H),1.14(m,1H). 13C NMR (101MHz, CDCl3) δ171.6,155.7,138.6,138.2,138.1,138.0,136.4,135.9,129.4,128.7,128.6,128.5,128.4,128.3,128.2,128.1 ,127.9,127.8,127.3,86.7,85.6,81.8,79.1,78.0,75.9,75.6,75.2,73.5,69.2,67.0,64.1,55.0,53.6,38.5,29.2,27.7.IR(neat,cm -1 )1732,1716,1496,1454,1274,1259,1060,1028,908,748,696.HRMS(ESI)m / z:[M+H] + Calcd for C 54 H 57 NO9S896.3832,Found 896.3822.

[0227] Example 49

[0228]

[0229] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (312.3 mg, 0.6 mmol, 3 equiv), BTMG (125 μL, 0.62 mmol, 3.1 equiv), and chloroform (2 mL). The mixture was reacted at 25°C for 16 hours. After completion, the reaction was dried and purified by column chromatography to afford 5ae (152.3 mg, 73%) as a white solid. 1 H NMR(400MHz, CDCl3)δ7.36(m,2H),7.35–7.21(m,16H),7.16(d,J=7.2Hz,2H) ,7.00(d,J=7.9Hz,2H),6.78(d,J=7.9Hz,2H),4.85(m,6H),4.52(dt,J=30.2 ,10.7Hz,5H),3.90(t,J=5.3Hz,2H),3.76–3.57(m,7H),3.45(m,1H),3.01(t ,J=6.0Hz,2H),2.80(m,2H),1.86(s,4H),1.41(s,9H),1.25(t,J=7.1Hz,3H). 13C NMR (101MHz, CDCl3) δ172.5,171.1,158.1,155.2,138.5,138.2,138.1,138.0,130.3,128.5,128.4,128.3,128.0,127.9,127.8,127.7,127.6, 114.6,86.7,85.3,81.9,79.1,78.0,75.8,75.5,75.1,73.5,69.1,67.3 ,60.4,54.6,52.2,37.5,30.7,28.4,28.3,26.6,21.1,14.2.IR(neat,cm -1 )2931,2866,1745,1712,1633,1526,1454,1365,1274,1244,1150,1058,1026,914,827,781,750,698.HRMS(ESI)m / z:[M+H] + Calcd for C 53 H 64 NO 10 S 906.4251,Found 906.4232.Mp:58.7–59.4℃.

[0230] Example 50

[0231]

[0232] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (273.2 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 evaporated to dryness and column chromatography afforded 5af (152.3 mg, 73%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.76–7.67(m,3H),7.46–7.28(m,19H),7.25–7.10(m,4H),4.90(m,4H),4.75(d,J=10.3Hz,1H),4.62–4.51(m,3H),4.33– 4.15(m,3H),3.92(d,J=4.9Hz,1H),3.87(m,4H),3.72–3.59(m,3H),3. 45–3.34(m,2H),2.66(m,2H),2.01–1.88(m,2H),1.61(d,J=7.0Hz,3H). 13C NMR (101MHz, CDCl3) δ174.6,157.7,138.6,138.2,138.0,135.8,133.7,129.4,129.0,128.5,128.4,128.3,128.0,127.9,127.8,127.7,127 .3,126.3,126.0,119.1,105.7,86.6,85.7,81.7,79.0,77.9,75.8,75.5,75.1,73.5,69.1,63.3,55.3,45.6,29.3,27.7,18.6.IR(neat,cm -1 )2868,1732,1606,1454,1263,1155,1064,1028,852,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 51 H 54 O8SNa 849.3437,Found 849.3416.

[0233] Example 51

[0234]

[0235] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (311.1 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 reacted at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5ag (131.7 mg, 74%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.53(d,J=7.3Hz,2H),7.46(d,J=7.2Hz,2H),7.28–7.12(m,24H),7.07(d,J=8.2Hz,2H),4.73(m,5H),4.45(m,3H),4. 33(d,J=9.9Hz,1H),4.13(t,J=6.1Hz,2H),3.77–3.47(m,4H),3.33m,2H),3.05(t,J=7.4Hz,2H),2.78(d,J=7.7Hz,4H),1.95–1.79(m,2H). 13C NMR (101MHz, CDCl3) δ171.9,161.8,145.5,138.5,138.2,138.1,138.0,135.2,132.5,129.0,128.7,128.6,128.5,128.4,128.3,128.1, 128.0,127.9,127.8,127.7,126.5,86.7,85.5,81.8,79.1,77.9,75.8,75.6,75.1,73.5,69.1,63.4,31.1,29.3,27.6,23.6.IR(neat,cm -1 )2868,2360,1734,1645,1496,1454,1373,1138,1060,763,750,692.HRMS(ESI)m / z:[M+H] + Calcdfor C 55 H 56 NO8S890.3727,Found 890.3713.

[0236] Example 52

[0237]

[0238] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (306.3 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 allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5ah (151.7 mg, 86%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ8.00(d,J=7.9Hz,2H),7.72(d,J=8.1Hz,2H),7.26–7.09(m,18H),7.04(d,J=7.4Hz,2H),5.11(s,1H),4.71(m,6H),4.48–4.28 (m,6H),3.54(m,4H),3.34(d,J=9.1Hz,2H),2.99–2.90(m,4H),2.76(m,2H ),2.07–1.98(m,2H),1.40(dd,J=14.8,7.4Hz,4H),0.73(t,J=7.3Hz,6H). 13C NMR (101MHz, CDCl3) δ165.2,144.3,138.5,138.2,138.0,137.9,133.6,130.3,128.5,128.4,128.1,128.0,127.9,127.8, 127.7,127.1,86.7,85.6,81.8,79.1,78.0,75.8,75.6,75.1,73.5,69.1,64.3,50.0,29.3,27.8,22.0,11.2.IR(neat,cm -1 )2868,2360,1718,1454,1344,1273,1157,1085,1066,991,748,732,601.HRMS(ESI)m / z:[M+Na] + Calcd for C 50 H 59 NO9S2Na 904.3529,Found 904.3517.

[0239] Example 53

[0240]

[0241] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (258.8 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 5ai (154.2 mg, 95%) as a colorless liquid. 1 H NMR(400MHz, CDCl3)δ7.25(d,J=6.8Hz,2H),7.23–7.11(m,16H),7.10–7.02(m,4H) ),6.96(d,J=7.7Hz,2H),4.73(m,4H),4.52–4.25(m,4H),4.05(t,J=6.1Hz,2H),3. 64–3.47(m,5H),3.31(t,J=8.6Hz,2H),2.65–2.48(m,1H),2.31(d,J=7.0Hz,2H),1 .88–1.80(m,1H),1.78–1.65(m,1H),1.36(d,J=6.8Hz,3H),0.77(d,J=6.5Hz,6H). 13C NMR (101MHz, CDCl3) δ174.7,140.6,138.6,138.3,138.2,138.0,137.9,129.5,128.6,128.5,128.4,128.1,127.9,127.8,127.7 ,127.3,86.8,85.6,81.8,79.2,78.0,75.9,75.6,75.1,73.5,69.1,63.2,45.1,30.3,29.4,27.6,22.5,18.6,18.5.IR(neat,cm -1 )2868,1732,1454,1201,1157,1085,1064,1028,748,732,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 50 H 58 O7SNa 825.3801,Found 825.3784.

[0242] Example 54

[0243]

[0244] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (208.4 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 was dried and column chromatography afforded 5aj (101.5 mg, 72%) as a yellow liquid. 1 H NMR (400MHz, CDCl3) δ7.38(d,J=7.4Hz,2H),7.29(m,16H),7.18–7.14(m,2H),4.94–4.73(m,6H),4.48(m,6H),3.76–3.60(m,5H),3.52–3.41( m,2H),3.01–2.91(m,1H),2.82–2.66(m,1H),2.54–2.40(m,1H),2.08( m,1H),1.86–1.46(m,7H),1.34–1.17(m,2H),0.94(s,3H),0.86(s,3H). 13C NMR (101MHz, CDCl3) δ138.5,138.3,138.1,138.0,128.5,128.4,128.0,127.9,127.8,127.6,86.8,85.0,81.8,79.2,78. 0,75.9,75.6,75.1,73.5,69.1,60.3,53.3,48.4,45.7,41.6,39.5,38.9,31.5,28.6,28.0,27.0,21.3,19.5.IR(neat,cm -1 )2868,1454,1083,1066,1028,999,748,732,692.HRMS(ESI)m / z:[M+H] + Calcd for C 45 H 53 O5S 705.3614, Found 705.3609.

[0245] Example 55

[0246]

[0247] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (324.9 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 5ak (151.6 mg, 83%) as a white solid. 1 H NMR (500MHz, CDCl3) δ8.19 (dd, J=8.4, 2.1Hz, 1H), 8.07 (m, 1H), 7.42 (m, 2H), 7.38–7.26(m,16H),7.24–7.15(m,2H),6.97(d,J=8.9Hz,1H),5.02–4.70(m, 5H),4.67–4.38(m,6H),3.90(d,J=7.1Hz,3H),3.81–3.63(m,4H),3.58–3.46 (m,2H),2.97(m,2H),2.80(s,3H),2.29–2.05(m,3H),1.12(d,J=6.7Hz,6H). 13C NMR (126MHz, CDCl3) δ167.3,162.5,161.9,161.3,161.3,138.5,138.2,138. 0,137.9,132.6,132.1,128.5,128.4,128.2,128.0,127.9,127.8,127.7,12 6.0,121.7,115.4,112.7,103.0,86.7,85.6,81.7,79.2,78.0,75.8,75.7,7 5.6,75.1,73.5,69.1,63.9,53.6,29.4,28.2,27.7,19.1,17.6.IR(neat,cm -1 )2360,1669,1506,1456,1328,1274,1089,1070,1012,763,750,694.HRMS(ESI)m / z:[M+H] + Calcd for C 53 H 57 N2O8S2913.3556,Found 913.3538.Mp:67.9–68.5℃.

[0248] Example 56

[0249]

[0250] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (326.2 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 allowed to react at 25°C for 16 hours. After the reaction was complete, the mixture was spin-dried and column chromatography yielded 5al (182.1 mg, 98%) as a colorless liquid. 1 H NMR (500MHz, CDCl3) δ7.47–7.27(m,18H),7.26–7.15(m,2H),6.54(dd,J=64.3,2.6Hz,2H),5.05–4.76(m,5H),4.70–4.45(m,4H),3.92(d,J=4. 7Hz,3H),3.85–3.63(m,4H),3.58–3.44(m,2H),2.84(m,4H),2.20(d,J= 4.1Hz,4H),1.99–1.73(m,7H),1.68–1.06(m,28H),1.01–0.83(m,12H). 13C NMR (126MHz, CDCl3) δ151.6,146.2,138.6,138.3,138.1,128.5,128.4,128.2,128.0 ,127.9,127.8,127.7,127.6,127.2,121.0,115.5,111.9,86.7,85.3,81.9,79.2,78 .0,75.8,75.6,75.1,73.5,69.1,67.8,40.1,39.5,37.5,37.4,32.9,32.8,31.5,30. 7,28.7,28.1,26.7,24.9,24.5,24.2,22.8,22.7,21.1,19.9,19.8,16.3.IR(neat,cm -1 )2924,1471,1454,1274,1215,1153,1085,1062,1028,908,763,750,731,696.HRMS(ESI)m / z:[M+Na] + Calcd for C 65 H 88 O7SNa 1035.6148,Found 1035.6147.

[0251] Example 57

[0252]

[0253] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (352.2 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 spin-dried and column chromatography afforded 5am (189.8 mg, 99%) as a white solid. 1H NMR (400MHz, CDCl3) δ7.54(d,J=8.2Hz,2H),7.24–7.14(m,19H),7.06(d,J=7.8Hz,2H ),6.95(d,J=8.1Hz,2H),6.67(d,J=8.1Hz,2H),6.60(d,J=5.0Hz,1H),4.84–4.52(m,5 H),4.49–4.33(m,3H),4.28(d,J=9.7Hz,1H),4.14(m,2H),3.74–3.42(m,6H),3.39–3 .22(m,2H),2.71(d,J=6.4Hz,2H),2.60–2.39(m,2H),1.90–1.77(m,2H),1.49(s,6H). 13 C NMR (101MHz, CDCl3) δ174.2,166.5,154.2,138.5,138.1,138.0,137.9,137.4,133.2,132.6,129.6,128.7,128.6,128.5,128.4,128.3,128.0,1 27.8,119.0,86.6,85.4,81.7,79.1,79.0,77.9,77.5,75.8,75.6,75.1 ,73.4,69.1,63.8,41.5,38.7,34.8,29.1,27.4,25.6,25.5.IR(neat,cm -1 )2868,2360,1724,1645,1508,1489,1276,1151,1091,1066,748,692.HRMS(ESI)m / z:[M+H] + Calcd for C 56 H 61 NO9SCl 958.3756,Found 958.3745.Mp:87.8–89.1℃.

[0254] Example 58

[0255]

[0256] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (322.6 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 mixture was spin-dried and column chromatography yielded 5an (121.6 mg, 69%) as a yellow liquid. 1H NMR(400MHz, CDCl3)δ7.37–7.21(m,17H),7.20(s,1H),7.18–7.10(m,3H), 6.64(m,2H),4.96–4.37(m,9H),4.01(t,J=6.3Hz,2H),3.86–3.55(m,4H),3 .42(m,2H),3.03–2.64(m,4H),2.47(dd,J=18.9,8.6Hz,1H),2.38–2.16(m, 2H),2.14–1.89(m,6H),1.64–1.32(m,7H),1.28–1.19(m,1H),0.87(s,3H). 13 C NMR (101MHz, CDCl3) δ157.0,138.6,138.3,138.1,137.8,132.1,128.5,128.4,128.3,128.0,127.8,127.6,126.4,114.7,112.3,86.7,85.6,81. 8,79.1,78.0,77.4,75.8,75.5,75.1,73.5,69.2,66.0,50.5,48.1,44.0 ,38.4,35.9,31.7,29.9,29.7,27.8,26.6,26.0,21.6,13.9.IR(neat,cm -1 )2902,2868,1734,1506,1496,1456,1278,1255,1155,1055,1028,1004,908,748,731,692.HRMS(ESI)m / z:[M+Na] + Calcd for C 56 H 64 O7SNa 903.4270,Found 903.4261.

[0257] Example 59

[0258]

[0259] To a reaction tube, add sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (349.7 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 the reaction is complete, the mixture is spin-dried and column chromatography yields 5ao (129.8 mg, 68%) as a yellow liquid. 11H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 6.6 Hz, 2H), 7.19 (m, 16H), 7.07 (d, J = 8.3 Hz, 2H), 6.87 (s, 1H), 6.76 (d, J = 8.8 Hz, 1H), 6.56 (dd, J = 8.9, 2.1 Hz, 1H), 5.13 (s, 1H), 4.86–4.60 (m, 5H), 4.51–4.25 (m, 4H), 4.12 (t, J = 6.1 Hz, 2H), 3.69 (s, 3H), 3.60–3.48 (m, 6H), 3.31 (t, J = 9.0 Hz, 2H), 2.63 (m, 2H), 2.27 (s, 3H), 1.91 (m, 2H). 13 13C NMR (101 MHz, CDCl3) δ 170.8, 168.3, 156.2, 139.2, 138.6, 138.2, 138.1, 138.0, 136.0, 134.0, 131.2, 130.9, 130.7, 129.2, 128.5, 128.4, 128.3, 128.2, 128.1, 128.0, 127.9, 127.8, 127.7, 115.1, 112.7, 111.8, 101.4, 86.6, 85.7, 81.8, 79.1, 78.0, 75.8, 75.6, 75.1, 73.5, 69.1, 63.6, 55.8, 53.6, 30.4, 29.3, 27.7, 13.5. IR (neat, cm -1 ) 2868, 2360, 1681, 1477, 1454, 1355, 1313, 1259, 1220, 1139, 1085, 1064, 908, 833, 752, 732, 692. HRMS (ESI) m / z: [M+H] + Calcd for C 56 H 57 NO9SCl 954.3443, Found 954.3427.

[0260] Example 60

[0261]

[0262] A sugar (108 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea (309.2 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 allowed to react at 25°C for 16 hours. After completion of the reaction, the mixture was spin-dried and column chromatography yielded 5ap (135.7 mg, 79%) as a yellow liquid. 1 H NMR(400MHz, CDCl3)δ7.36(m,5H),7.35–7.27(m,13H),7.21–7.14(m,2H), 5.48(m,1H),4.94(m,3H),4.90–4.84(m,3H),4.84–4.75(m,2H),4.70–4.4 5(m,4H),4.08(m,1H),3.79–3.66(m,4H),3.47(dd,J=5.4,4.1Hz,1H),3.3 6(s,3H),2.94(m,1H),2.81(m,1H),2.09(s,3H),2.03(s,3H),2.01(s,3H). 13 C NMR (101MHz, CDCl3) δ170.2,170.1,169.8,138.5,138.2,138.1,138.0,128.5,128.4,128.2,127.9,127.8,127.7,96.4,86 .7,85.7,82.2,79.0,77.9,77.4,75.8,75.5,75.0,73.5,72.2,71.1,70.2,70.1,68.9,55.4,31.8,20.8,20.7.IR(neat,cm -1 )2932,2866,1716,1494,1458,1365,1211,1158,1068,1028,908,748,732,694.HRMS(ESI)m / z:[M+Na] + Calcdfor C 47 H 54 O 13 SNa881.3183,Found 881.3170.

[0263] Example 61

[0264]

[0265] To a reaction tube, add sugar (281 mg, 0.2 mmol, 1 equiv), tetramethylalkylthiourea reagent (226.4 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, spin-dry the mixture and column chromatography yielded 5aq (304.5 mg, 96%) as a colorless liquid. 1 H NMR (400MHz, CDCl3) δ7.50–7.27(m,92H),6.87–6.81(m,2H),6.80–6.72(m,3H),5.40(d,J=5.4Hz,1H,α),5. 24(d,J=3.5Hz,1H,β),5.10(d,J=3.5Hz,1H),5.06–4.97(m,6H),4.96–4.85(m,9H),4.85–4.81(m,3H),4.80 –4.68(m,9H),4.68–4.61(m,7H),4.61–4.43(m,7H),4.21–4.08(m,9H),4.08–3.89(m,11H),3.89–3.84(m,6 H),3.81(dd,J=9.9,6.1Hz,6H),3.78–3.62(m,9H),3.53–3.46(m,1H),3.26–3.19(m,1H),3.01–2.87(m,6H). 13 C NMR (101MHz, CDCl3) δ149.0,147.8,139.0,138.9,138.8,138.7,138.5,138.2,138.1,133.2,133.1,128.7,128.5,128.4,128 .3,128.2,128.1,128.0,127.9,127.8,127.7,127.6,127.5,127.4,120.7,112.1,112.0,111.4,98.3,98.2,97.9,86.6,85.7 ,83.3,82.5,81.8,80.0,79.4,79.3,78.5,78.4,77.8,76.7,76.5,75.7,75.5,75.4,75.3,75.1,75.0,74.9,74.8,73.7,73.6 ,72.9,72.8,72.7,72.6,72.3,71.4,69.6,69.2,69.1,68.9,66.8,66.7,66.6,65.8,55.9,36.5,35.9,32.8,31.2.IR(neat,cm -1)2923,2865,1418,1404,1351,1206,1158,1070,1028,908,748,732,694.HRMS(ESI)m / z:[M+Na] + Calcd for C 98 H 104 O 17 SNa 1607.6892, Found 1607.6886.

[0266] Example 62

[0267]

[0268] A glucosinolate (57.1 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (2 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 afforded a colorless liquid 6a (56.1 mg, 93%). 1 H NMR (400MHz, CDCl3) δ7.38–7.33(m,2H),7.32–7.21(m,16H),7.18–7.13(m,2H),4.93–4.71(m,5 H),4.56(q,J=12.3Hz,3H),4.35(d,J=9.7Hz,1H),3.68(m,4H),3.50–3.40(m,2H),2.22(s,3H). 13 C NMR (101MHz, CDCl3) δ138.6,138.3,138.2,138.1,128.5,128.4,128.0,127.9,127.8 ,127.7,86.7,85.4,81.3,79.3,78.1,75.8,75.5,75.1,73.6,69.1,13.0.IR(neat,cm -1 )2906,2868,1496,1452,1363,1130,1085,1066,1055,1028,948,887,756,732,692.

[0269] Example 63

[0270]

[0271] A glucosinolate compound (61.3 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (2 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 (61.2 mg, 95%). 1 H NMR (400MHz, CDCl3) δ7.28–7.20(m,18H),7.12–7.07(m,2H),4.93(d,J=9.7Hz,1H),4.88(d ,J=11.1Hz,1H),4.81(d,J=11.1Hz,1H),4.72(dd,J=12.6,10.5Hz,2H),4.49(d,J=10.8Hz,1 H),4.45(s,2H),4.29(d,J=9.3Hz,1H),4.03(t,J=9.1Hz,1H),3.72(t,J=8.5Hz,1H),3.65–3 .47(m,4H),3.12–2.92(m,2H),1.82–1.68(m,2H),1.36–1.29(m,2H),0.83(t,J=7.2Hz,3H). 13 C NMR (101MHz, CDCl3) δ138.17,137.85,137.62,137.46,128.73,128.57,128.55,128.48,128.45,128.12,128.06,12 8.01,127.84,127.75,127.68,89.34,86.17,79.85,75.96,75.48,75.23,73.43,68.73,50.99,23.30,21.83,13.59.

[0272] Example 64

[0273]

[0274] A glucosinolate (64.1 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (2 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 (59.9 mg, 89%). 1H NMR (400MHz, CDCl3) δ7.32–7.19(m,18H),7.12–7.07(m,2H),4.92(d,J=9.7Hz,1H),4.88(d, J=11.1Hz,1H),4.81(d,J=11.1Hz,1H),4.73(t,J=10.9Hz,2H),4.49(d,J=10.9Hz,1H),4.46( s,2H),4.30(d,J=9.3Hz,1H),4.03(t,J=9.1Hz,1H),3.73(t,J=8.6Hz,1H),3.62(d,J=10.2Hz ,1H),3.53(m,3H),3.11–2.92(m,2H),1.75(m,2H),1.25–1.15(m,6H),0.79(t,J=6.8Hz,3H). 13 C NMR (101MHz, CDCl3) δ138.16,137.84,137.61,137.45,128.73,128.57,128.55,128.49,128.46,128.12,128.06,128.01,1 27.85,127.75,127.68,89.33,86.16,79.84,75.96,75.48,75.24,73.43,68.70,51.27,31.22,28.26,22.38,21.29,14.01.

[0275] Example 65

[0276]

[0277] A glucosinolate compound (61.1 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (2 mL) were added to a reaction tube and reacted at 25°C for 8 hours. After the reaction was complete, the product was dried and purified by column chromatography to afford a colorless liquid, 6d (59.8 mg, 93%). 1H NMR (400MHz, CDCl3) δ7.30–7.19(m,18H),7.12–7.06(m,2H),5.69(m,1H),5.07–4.96(m,2H),4.93 (d,J=9.7Hz,1H),4.88(d,J=11.1Hz,1H),4.80(d,J=11.1Hz,1H),4.72(dd,J=12.4,10.5Hz,2H),4. 51–4.47(m,1H),4.45(s,2H),4.31(d,J=9.4Hz,1H),4.04(t,J=9.1Hz,1H),3.72(t,J=8.4Hz,1H),3 .62(d,J=10.1Hz,1H),3.57–3.45(m,3H),3.24–3.13(m,1H),3.11–2.99(m,1H),2.62–2.44(m,2H). 13 C NMR (101MHz, CDCl3) δ138.13,137.75,137.56,137.39,128.75,128.57,128.55,128.51,128.46,128.1 4(s),127.87,127.81,127.68,117.29,89.59,86.11,79.73,75.97,75.52,75.26,73.43,68.67,50.43.

[0278] Example 66

[0279]

[0280] A glucosinolate compound (66.1 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (2 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 6e (65.8 mg, 95%). 1H NMR (400MHz, CDCl3) δ7.37–7.34(m,2H),7.31–7.24(m,16H),7.21(m,3H),7.16–7.11(m,4H),4.99( d,J=9.7Hz,1H),4.92(d,J=11.1Hz,1H),4.85(d,J=11.2Hz,1H),4.77(dd,J=10.3,5.0Hz,2H),4.53 (d,J=10.9Hz,1H),4.50(s,2H),4.21(d,J=9.3Hz,1H),4.09(t,J=9.1Hz,1H),3.73(t,J=8.9Hz,1H) ,3.62–3.52(m,3H),3.51–3.44(m,1H),3.37(dd,J=9.2,4.3Hz,1H),3.32–3.23(m,1H),3.11(m,2H). 13 C NMR (101MHz, CDCl3) δ138.15,137.74,137.72,137.56,137.42,128.85,128.75,128.67,128.58,128.52,128.48 ,128.18,127.87,127.83,127.68,89.57,86.07,79.77,76.98,75.96,75.53,75.29,73.43,68.50,52.60,28.09.

[0281] Example 67

[0282]

[0283] A glucosinolate (74.4 mg, 0.1 mmol, 1 equiv), m-CPBA (61 mg, 0.25 mmol, 2.5 equiv), and chloroform (2 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 (74.5 mg, 96%) as a colorless liquid. 1H NMR (400MHz, CDCl3) δ7.78–7.71(m,2H),7.62(m,2H),7.29–7.26(m,4H),7.24–7.17(m,14H),7.1 1–7.06(m,2H),4.90(d,J=10.1Hz,1H),4.84(d,J=14.7Hz,1H),4.77(dd,J=15.5,3.5Hz,1H),4.7 0(dd,J=12.9,3.4Hz,2H),4.49(d,J=10.9Hz,1H),4.44–4.34(m,3H),4.02(t,J=8.7Hz,1H),3.73 (t,J=8.6Hz,1H),3.67(t,J=6.7Hz,2H),3.62–3.49(m,4H),3.24–3.00(m,2H),2.26–2.07(m,2H). 13 C NMR (101MHz, CDCl3) δ168.16,138.16,137.83,137.64,137.41,128.70,128.63,128.56,128.53,128.46,128.44,128.40,128.10,12 8.05,127.89,127.85,127.78,127.72,127.67,89.60,86.08,79.80,76.98,75.95,75.48,75.22,73.38,68.53,49.18,36.48,21.39.

[0284] 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.

[0285] 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.

[0286] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0287] 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 tetramethylalkylthiourea reagent, characterized in that The structure of the tetramethylalkylthiourea reagent is shown in the following formula (3): in, R 1 Selected from primary alkyl, secondary alkyl, tertiary alkyl, allyl, propargyl, benzyl, and alkyl containing active molecules; wherein the active molecules are selected from amino acids, isoxacic acid, naproxen, opsaqin, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, and indomethacin; X is selected from bromine and iodine.

2. A method for synthesizing a tetramethylalkylthiourea reagent, characterized in that: Tetramethylthiourea represented by formula (1) and an alkyl halide represented by formula (2) are used as reaction raw materials, and react in an organic solvent to obtain a tetramethylalkylthiourea reagent represented by formula (3). The reaction process is shown in reaction formula (a); in, R 1 Selected from primary alkyl, secondary alkyl, tertiary alkyl, allyl, propargyl, benzyl, and alkyl containing active molecules; wherein the active molecules are selected from amino acids, isoxacic acid, naproxen, opsaqin, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, and indomethacin; X is selected from bromine and iodine.

3. The synthesis method according to claim 2, wherein The ratio of the tetramethylthiourea represented by formula (1), the alkyl halide represented by formula (2) and the organic solvent is 1 mol: (2-3) mol: (5-20) volume; and / or, The organic solvent is selected from one or more of ethanol, methanol, and tert-butanol; and / or the reaction temperature is 25-70° C.; and / or the reaction time is 8-16 hours.

4. A use of a tetramethylalkylthiourea reagent in the selective construction of glucosidic compounds, characterized in that: The sugar represented by formula (4) and the tetramethylalkylthiourea 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, R 2 Selected from benzyl, acyl, silicon; R 1 Selected from primary alkyl, secondary alkyl, tertiary alkyl, allyl, propargyl, benzyl and alkyl containing active molecules; wherein the active molecules are selected from amino acids, isoxacic acid, naproxen, opsazone, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, indomethacin; X is selected from bromine and iodine; n is selected from an integer of 3-4.

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 tetramethylalkylthiourea reagent is 1 mol: (1.5 to 3.1) mol: (5 to 20) volume: (1.5 to 3) mol.

7. Use of a glucosinolate compound in selectively 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 carried out to obtain an oxidized glucosinolate compound represented by formula (6). The reaction process is shown in reaction formula (c): in, R 2 Selected from benzyl, acyl, silicon; R 1 Selected from primary alkyl, secondary alkyl, tertiary alkyl, allyl, propargyl, benzyl and alkyl containing active molecules; wherein the active molecules are selected from amino acids, isoxacic acid, naproxen, opsaqin, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, indomethacin; n is selected from an integer of 3-4.

8. The use according to claim 7, characterized in that The ratio of the glucosidic compound represented by formula (5) to the oxidant and the organic solvent is 1 mol:(2-3) mol:(5-20) volume; and / or, the organic solvent is selected from one or more of chloroform, dichloromethane, methanol, and ethanol; and / or, the oxidant is selected from one or two 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 The structure of the glucosinolate compound is shown in formula (5): in, R 2 Selected from benzyl, acyl, silicon; R 1 Selected from primary alkyl, secondary alkyl, tertiary alkyl, allyl, propargyl, benzyl and alkyl containing active molecules; wherein the active molecules are selected from amino acids, isoxacic acid, naproxen, opsaqin, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, indomethacin; n is selected from an integer of 3-4.

10. An oxidized sulfosuccinoside compound, characterized in that: The structure of the oxidized glucosinolate compound is shown in formula (6): in, R 2 Selected from benzyl, acyl, silicon; R 1 Selected from primary alkyl, secondary alkyl, tertiary alkyl, allyl, propargyl, benzyl and alkyl containing active molecules; wherein the active molecules are selected from amino acids, isoxacic acid, naproxen, opsaqin, probenecid, ibuprofen, noprofen, febuxostat, tocopherol, bezafibrate, estrone, indomethacin; n is selected from an integer of 3-4.

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