Glucoside substance and preparation method thereof

Abstract

The invention discloses a glycoside substance and a preparation method thereof. The preparation method of the glycoside substance comprises the following steps: in a protective atmosphere, enabling carbohydrates, a nucleophilic reagent, an activating agent, a metal catalyst and an additive to react in an organic solvent to generate a glycoside product. The synthesis strategy of the invention is a method for generating a glycosylation product by taking thiosugar as a sugar donor, taking a nucleophilic reagent as a sugar receptor and taking a 3-substituted 1, 4, 2-dioxazole-5-ketone substance as an activating agent through reaction under the condition of a metal catalyst. The synthesis strategy has universality and is suitable for various metal catalytic systems. The reaction system is efficient. In addition, a cheap iron catalyst can be used, and the dosage of the catalyst can be as low as 0.5%. The strategy is mild. Finally, the method does not use or only uses a catalytic amount of acid additive, so that the method is compatible with weak nucleophilic reagents such as phosphoric acid, amide, uracil and the like, and is suitable for glycosylation of weak nucleophilic receptors.

Description

Technical Field

[0001] The present invention relates to the technical field of sugar chemical synthesis, and more particularly to glycoside substances and preparation methods thereof. Background Art

[0002] Sugar compounds are one of the most abundant compounds in nature and play an important role in synthetic chemistry, medicine, life sciences and agricultural food. Although glycoside molecules have a wide range of applications, their chemical synthesis still faces great challenges due to the structural characteristics of sugar compounds with multiple hydroxyl groups and multiple chiral centers. The construction of glycosidic bonds is the core issue in the synthesis of sugar compounds.

[0003] Sulfosaccharides are one of the most popular sugar donors due to their relative stability and unique activation mode. Traditional thiosaccharide activation usually requires the use of an equivalent amount of Lewis acid or Bronsted acid as an activator, and the strong acidic conditions limit its applicability. In contrast, metal-catalyzed glycosidation reactions are relatively mild and are gradually favored by chemists. There are usually three types of metal-catalyzed glucosidase activation: direct activation, relay activation, and synergistic activation. Direct activation is to use the Lewis acidity of the metal to coordinate with sulfur to activate thiosaccharides. It requires the use of precious metals such as Ag, Bi, In, Au, etc. Due to the coordination poisoning effect of sulfur atoms, the catalytic conversion number of the catalyst is low. Relay activation requires the use of pre-designed sugar donors, and the introduction of active groups such as alkenyl and alkynyl groups at the distal end. The metal first reacts with the active group and activates the thiosaccharide by relay. The problem with relay activation is that relatively complex sugar donors need to be prepared in advance. Synergistic activation is to add an additional co-activator under metal catalysis. The catalyst first reacts with the co-activator to generate a new active intermediate, which further participates in the activation of thiosaccharides. For example, Wan Qian's research group at Huazhong University of Science and Technology developed a rhodium-catalyzed carbene-involved glycosidation reaction. The reaction first involves the reaction of a diazotide with a rhodium catalyst to form a rhodium carbene, followed by the reaction of the rhodium carbene with thioglucose to form a thioylide. The intermediate forms an oxonium intermediate under acid catalysis, which then reacts with a sugar acceptor to obtain a glycosidation product. Although the reaction is very efficient, it requires the use of a noble metal rhodium catalyst and a relatively unstable diazotide. In addition to the above problems, with thioglucose as the sugar donor, metal-catalyzed glycosidation reactions mainly use alcohols, carboxylic acids and phenols as sugar acceptors, while the compatibility with weak nucleophilic sugar acceptors such as amides, pyrimidines, and phosphoric acids is relatively poor. In summary, although transition metal-catalyzed glucosidation has made great progress, there are still problems in this field: 1. There is a lack of a simple and universal metal-catalyzed glycosidation system; 2. There is a lack of an efficient and inexpensive metal catalytic system; 3. There are still few glycosidation strategies suitable for weak nucleophilic acceptors;

[0004] Therefore, it is necessary to develop a better method for synthesizing glycosides. Summary of the invention

[0005] In order to solve the problems in the prior art, the present invention proposes glycoside substances and preparation methods thereof. The synthesis strategy of the present invention is to use thioglucose as a sugar donor, a nucleophilic reagent as a sugar acceptor, and a 3-substituted 1,4,2-dioxazol-5-one substance as an activator, and react under the condition of a metal catalyst to generate a method for glycosylation products. This synthesis strategy is versatile and applicable to a variety of metal catalytic systems. The reaction system is efficient. In addition, the present invention can use a cheap iron catalyst, and the catalyst dosage can be as low as 0.5%. The strategy is mild. Finally, the present invention does not use or only uses a catalytic amount of an acid additive, so that it is compatible with weak nucleophiles such as phosphoric acid, amides, uracil, etc., and is suitable for the glycosylation of weak nucleophilic acceptors.

[0006] One of the purposes of the present invention is to provide a method for preparing glycoside substances mediated by metal catalysis nitrene, comprising the following steps: under a protective atmosphere, reacting a sugar substance, a nucleophilic reagent, an activator, a metal catalyst and an additive in an organic solvent to generate a glycoside product.

[0007] As a preferred embodiment,

[0008] The carbohydrate substance is selected from at least one of the substances represented by the general structural formula of Formula I: Wherein, X is a heteroatom or a heteroatom group, preferably S or -S=O;

[0009] Ar is selected from substituted or unsubstituted aryl; preferably phenyl, alkyl or alkoxy substituted phenyl; more preferably phenyl, C1-C6 alkyl or C1-C6 alkoxy substituted phenyl; n is 0 or 1;

[0010] The R1 is selected from or at least one of the alkyl groups, m is an integer of 1-4; preferably, the R1 is at least selected from *-OBn; further preferably, the R1 is selected from *-OBn and selected from or at least one of C1-C3 alkyl groups; m is an integer of 2-4;

[0011] Further preferably, the carbohydrate substance is selected from at least one of the following substances:

[0012]

[0013] As a preferred embodiment, the nucleophile is selected from at least one of a hydroxyl-containing nucleophile, a carboxyl-containing nucleophile, a phosphate-containing nucleophile, an amide-containing nucleophile or a pyrimidine-containing nucleophile;

[0014] Preferably, the nucleophile is selected from Nu-H or At least one of the substances shown; wherein Nu is a nucleophilic group obtained by removing the hydrogen atom from a hydroxyl-containing nucleophile, a carboxyl-containing nucleophile, a phosphate-containing nucleophile, or an amide-containing nucleophile; R3 is hydrogen, nitro, or a C1-C3 alkyl group; preferably, R3 is selected from hydrogen, nitro, or methyl;

[0015] Further preferably, the nucleophilic agent is selected from at least one of the following substances:

[0016]

[0017] As a preferred embodiment, the activator is selected from at least one of the substances represented by the general structural formula of formula III: Wherein, the R2 is selected from an alkyl group, a substituted or unsubstituted aryl group; preferably, the R2 is selected from a C1-C10 alkyl group, a phenyl group or a C1-C6 alkoxy-substituted phenyl group; further preferably, the R2 is selected from a C1-C6 alkyl group, a phenyl group or a C1-C3 alkoxy-substituted phenyl group; further preferably, the activator is selected from at least one of the following substances:

[0018]

[0019] As a preferred embodiment, the metal catalyst is selected from at least one of an iron catalyst, a ruthenium catalyst or an iridium catalyst; preferably, the metal catalyst is selected from iron phthalocyanine (PcFe), ferric phthalocyanine chloride (PcFeCl), ferrous iodide (FeI2), dichlorobis(4-methylisopropylphenyl)ruthenium ([Ru(p-cymene)Cl2]2) or dichloro(pentamethylcyclopentadienyl)iridium dimer ([IrCp*Cl2]2); and / or,

[0020] The additive is selected from at least one of 2,6-di-tert-butylpyridine hydrochloride, 2,4,6-tri-tert-butylpyridine hydrochloride, 2,6-di-tert-butylpyridine trifluoromethanesulfonate, D-camphorsulfonic acid, L-camphorsulfonic acid, p-toluenesulfonic acid, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, silver hexafluorophosphate or silver tetrafluoroborate; and / or,

[0021] The organic solvent is selected from at least one of hexafluoroisopropanol, dichloromethane, toluene, tetrahydrofuran or acetonitrile.

[0022] As a preferred embodiment, the molar ratio of the sugar substance to the nucleophile is (1-4.5): (1-1.5); and / or,

[0023] The molar ratio of the sugar substance to the activator is (1-4.5): (1.5-4.5).

[0024] As a preferred embodiment, the molar ratio of the sugar substance or the nucleophilic reagent to the metal catalyst is (1-4.5): (0.005-0.1); and / or,

[0025] The molar ratio of the sugar substance or the nucleophilic reagent to the additive is (1-4.5): (0.05-0.1); and / or,

[0026] The reaction temperature is 25°C to 65°C; and / or,

[0027] The reaction time is 1 to 24 hours.

[0028] The second aspect of the present invention is to provide a glycoside substance prepared by the method described in the first aspect of the present invention, wherein the glycoside substance is selected from at least one of the substances represented by the general structural formula of Formula IV or Formula V:

[0029]

[0030] Wherein, n in the general structural formula of Formula IV or Formula V is independently 0 or 1;

[0031] R1 in the general formula of structures 1-4 of formula IV or formula V is independently selected from or at least one of the alkyl groups, m is an integer; preferably, the R1 is at least selected from *-OBn; further preferably, the R1 is selected from *-OBn and selected from or at least one of C1-C3 alkyl groups; m is an integer of 2-4; Nu in formula IV is selected from the nucleophilic group after the hydrogen atom is removed from the nucleophilic reagent;

[0032] In Formula V, R3 is hydrogen, nitro or C1-C3 alkyl; R3 is selected from hydrogen, nitro or methyl. As a preferred embodiment, Nu is selected from the following groups:

[0033]

[0034] As a preferred embodiment, the glycoside substance is selected from at least one of the following substances:

[0035]

[0036] The endpoints and any values ​​of the scope disclosed in the present invention are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values. For numerical ranges, the endpoint values ​​of each scope, the endpoint values ​​of each scope and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be regarded as specifically disclosed in this article.

[0037] The present invention has the following advantages:

[0038] The inventor of the present invention thinks that nitrene is a class of electron-deficient amination intermediates, which are commonly used in CH bond amination and olefin amination. In addition, the heteroatom amination strategy in which nitrene participates has been rapidly developed in recent years, especially the nitrene-mediated thioether amination reaction. After thioether amination, sulfilimine is obtained, and such products are due to the strong electronegativity of nitrogen, so sulfilimine can resonate as sulfur nitrogen ylide, and sulfur has a strong positive charge. Therefore, sulfilimine based on thiosugar has a strong positive charge due to the sulfur atom in the anomeric position, which is easy to form an oxonium intermediate, and then glycosidation reaction occurs with sugar receptors. And the development of cheap metal catalysis and nitrene-mediated thioether amination reaction is relatively mature, and its nitrene precursor is easy to obtain, the reaction is efficient, and the conditions are mild, which is a class of excellent glycosidation reaction strategies. The mild reaction conditions of the present invention provide favorable conditions for the glycosidation reaction of weak nucleophiles such as amides, phosphoric acid, and uracil, so this strategy has a high application value. DETAILED DESCRIPTION

[0039] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0040] It should also be noted that the various specific technical features described in the following specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0041] In addition, the various embodiments of the present invention may be arbitrarily combined as long as they do not violate the concept of the present invention. The technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0042] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0043] A metal-catalyzed nitrene-mediated glycosidation reaction has the following general reaction formula:

[0044]

[0045] The method A is as follows: a carbohydrate substance of formula I (1.5 equivalents) and D-camphorsulfonic acid (D-CSA, 5 mol%, i.e., D-camphorsulfonic acid is added as an additive at 5% of the molar amount of the nucleophilic agent) are added to a hexafluoroisopropanol (HFIP) solvent, followed by sequentially adding nucleophilic agents of formula II (1.0 equivalents), PcFe (0.1 mol%), and formula III (1.5 equivalents), wherein the concentration of the nucleophilic agent of formula II is 0.2 mol / L, and the reaction system is reacted at 25° C. in a nitrogen atmosphere for 12 hours. After the reaction is completed, the reaction solvent is dried by spin drying, and the remaining mixture is separated by silica gel column chromatography to obtain glycosylated products of formula IV (products D1, D3-D5, D7-D12, D16-D20).

[0046]

[0047] The method B is as follows: a carbohydrate substance of formula I (1.0 equivalent), [Ru(p-cymene)Cl2]2 (5 mol%), and NaBArF4 (10 mol%) are added to a dichloromethane solvent, followed by sequential addition of a nucleophilic reagent (formula II, 1.5 equivalents) and formula III (3.0 equivalents), wherein the concentration of formula I is 0.2 mol / L, and the reaction system is reacted at 50° C. in a nitrogen atmosphere for 24 hours. After the reaction is completed, the reaction solvent is dried, and the remaining mixture is separated by silica gel column chromatography to obtain a glycosylated product of formula IV (products D2, D6, D13-D15, D21-D29).

[0048]

[0049] Method C: Add the carbohydrate substance Formula I (1.0 equivalent), [Ru(p-cymene)Cl2]2 (5 mol%), and NaBArF4 (10 mol%) to a dichloromethane solvent, and then add a nucleophile (Formula VI, 1.5 equivalents) and Formula III (3.0 equivalents) in sequence, wherein the concentration of Formula I is 0.2 mol / L, and the reaction system is reacted at 50°C in a nitrogen atmosphere for 24 hours. After the reaction is completed, the reaction solvent is dried, and the remaining mixture is separated by silica gel column chromatography to obtain a glycosylated product Formula V (product D30-D32).

[0050] In the method AC, the carbohydrate substance is selected from at least one of the substances represented by the general structural formula of formula I: Wherein, X is a heteroatom or a heteroatom group, preferably S or -S=O;

[0051] Ar is selected from substituted or unsubstituted aryl; preferably phenyl, alkyl or alkoxy substituted phenyl; further preferably phenyl, C1-C6 alkyl or C1-C6 alkoxy substituted phenyl; said n is 0 or 1;

[0052] The R1 is selected from or at least one of the alkyl groups, m is an integer of 1-4; preferably, the R1 is at least selected from *-OBn; further preferably, the R1 is selected from *-OBn and selected from or at least one of C1-C3 alkyl groups; m is an integer of 2-4;

[0053] Further preferably, the carbohydrate substance is selected from at least one of the following substances:

[0054]

[0055] The nucleophile is selected from at least one of a hydroxyl-containing nucleophile, a carboxyl-containing nucleophile, a phosphate-containing nucleophile, an amide-containing nucleophile, and a pyrimidine-containing nucleophile;

[0056] Preferably, the nucleophile is selected from Nu-H or At least one of the substances shown; wherein Nu is a nucleophilic group obtained by removing the hydrogen atom from a hydroxyl-containing nucleophile, a carboxyl-containing nucleophile, a phosphate-containing nucleophile, or an amide-containing nucleophile; R3 is hydrogen, nitro, or a C1-C3 alkyl group; preferably, R3 is selected from hydrogen, nitro, or methyl;

[0057] Further preferably, the nucleophilic agent is selected from at least one of the following substances:

[0058]

[0059]

[0060] The activator is selected from at least one of the substances represented by the general structural formula of formula III: Wherein, the R2 is selected from an alkyl group, a substituted or unsubstituted aryl group; preferably, the R2 is selected from a C1-C10 alkyl group, a phenyl group or a C1-C6 alkoxy-substituted phenyl group; further preferably, the R2 is selected from a C1-C6 alkyl group, a phenyl group or a C1-C3 alkoxy-substituted phenyl group; further preferably, the activator is selected from at least one of the following substances:

[0061]

[0062] The synthesized glycosylation product of formula IV exists in a single stereo configuration or diastereoisomer form. The synthesis method and detection data are as follows:

[0063] The metal catalyst is selected from at least one of an iron catalyst, a ruthenium catalyst or an iridium catalyst; preferably, the metal catalyst is selected from at least one of iron phthalocyanine, ferric phthalocyanine chloride, ferrous iodide, dichlorobis(4-methylisopropylphenyl)ruthenium or dichloro(pentamethylcyclopentadienyl)iridium dimer; and / or,

[0064] The additive is selected from at least one of 2,6-di-tert-butylpyridine hydrochloride, 2,4,6-tri-tert-butylpyridine hydrochloride, 2,6-di-tert-butylpyridine trifluoromethanesulfonate, D-camphorsulfonic acid, L-camphorsulfonic acid, p-toluenesulfonic acid, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, silver hexafluorophosphate or silver tetrafluoroborate; and / or,

[0065] The organic solvent is selected from at least one of hexafluoroisopropanol, dichloromethane, toluene, tetrahydrofuran or acetonitrile.

[0066] Embodiment 1-35

[0067]

[0068] Using F1, G1, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol scale was added (i.e., 1 equivalent represents 0.2 mmol, the same applies to the following examples, which are not repeated here), and finally the β-configuration product D1 (111.9 mg) was obtained. D1 is an unknown compound, a colorless oil (R f =0.6, petroleum ether / ethyl acetate=5:1). 1 H NMR (400MHz, CDCl3) δ7.37–7.26(m,13H),7.22–7.12(m,4H),7.00–6.91(m,2H),5.01(dd,J=9.1,8.0Hz,1H),4.80(dd,J=11.1,3.0Hz,2 H),4.71–4.50(m,4H),4.35(d,J=8.0Hz,1H),4.15–4.08(m,1H),3.79–3.55(m,5H),3.52–3.45(m,1H),2.93–2.79(m,2H),1.84(s,3H). 13CNMR(101MHz, CDCl3)δ169.54,161.60(d,J=243.9Hz),138.25,138.17,137.95,134.66,134.63,130.61,130.54,128.56,128.50,128.15 ,128.00,127.96,127.87,127.77,115.18,114.97,100.99,83.01,78 .10,75.26,75.17,75.13,73.62,73.06,70.16,68.85,35.33,20.93. 19 F NMR(376MHz,CDCl3)δ-117.25.HRMS(ESI)m / z Calcd for C 37 H 39 F7 + [M+Na] + :637.2572,found:637.2571.

[0069] The specific reaction conditions corresponding to Examples 1-35 are shown in Table 1.

[0070]

[0071]

[0072]

[0073]

[0074] Embodiment 36

[0075] Using F4, G1, and H1 as raw materials, according to the synthesis steps of method B, 0.2 mmol was added, and finally the product D2 (116.7 mg) was obtained with a yield of 88% and α:β=1.5:1. D2 is an unknown compound, a colorless oil (R f =0.6, petroleum ether / ethyl acetate=10:1). 1H NMR (400MHz, CDCl3) δ7.38–7.23(m,17H),7.21–7.11(m,5H),6.96–6.86(m,2H),4.9 8(d,J=10.8Hz,0.6H),4.91(d,J=10.9Hz,0.4H),4.86–4.77(m,2H),4.75(d,J=3.7Hz ,0.6H,H1-α),4.75–4.70(m,1H),4.64–4.41(m,4H),4.40(d,J=7.8Hz,0.4H,H1-β), 4.21–4.14(m,0.4H),3.97(t,J=8.9Hz,0.6H),3.84–3.39(m,7H),2.97–2.84(m,2H). 13 C NMR (101MHz, CDCl3) δ161.65 (d, J = 243.5Hz), 138.92, 138.68, 138.51, 138.42, 138.38, 138.21, 138.16, 137.99, 13 4.53,134.50,130.56,130.49,130.44,130.37,129.85,129.10,128.54,128.50,128.47,128.42,128.09,128.02,1 27.97,127.90,127.87,127.78,127.75,127.71,115.35,115.13,103.69,96.97,84.76,82.32,82.04,80.11,77.95,77.75,75.77,75.12,75.03,74.95,74.81,73.59,73.54,73.31,70.63,70.33,69.03,68.79,68.56,35.54,35.27. 19 F NMR(376MHz,CDCl3)δ-116.83.HRMS(ESI)m / zCalcd for C 42 H 43 F6Na + [M+Na] + :685.2936,found:685.2934.

[0076] Embodiment 37

[0077] Using F1, G2, and H1 as raw materials, according to the synthesis steps of method A (reaction temperature 50 degrees Celsius), 0.2mmol scale was added, and finally the product D3 (102.9mg) was obtained with a yield of 80% and β configuration. D3 is an unknown compound, a colorless oil (Rf =0.65, petroleum ether / ethyl acetate=10:1). 1 H NMR(400MHz, CDCl3)δ7.37–7.26(m,13H),7.22–7.19(m,2H),5.11–5.05(m,1H) ,4.80(d,J=10.8Hz,1H),4.79(d,J=11.5Hz,1H),4.67(d,J=11.5Hz,1H),4.60( d,J=12.3Hz,1H),4.59(d,J=10.4Hz,1H),4.58(d,J=8.1Hz,1H),4.55(d,J=12. 4Hz,1H),4.49–4.38(m,1H),3.76–3.63(m,4H),3.55–3.49(m,1H),1.96(s,3H). 13 C NMR (101MHz, CDCl3) δ169.29,138.12,138.05,137.76,128.61,128.57,128.21,128.12,127. 96,127.84,127.65,101.59,82.45,77.48,75.90,75.26,75.13,73.63,72.59,68.51,20.60. 19 F NMR(376MHz, CDCl3)δ-73.42(q,J=9.0Hz),-73.82(q,J=9.1Hz).HRMS(ESI)m / zCalcd for C 32 H 32 F6O7Na + [M+Na] + :665.1944,found:665.1945.

[0078] Embodiment 38

[0079] Using F4, G2, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D4 (82.9 mg) was obtained with a yield of 60% and α configuration. D4 is an unknown compound, a colorless oil (R f =0.7, petroleum ether / ethyl acetate=5:1). 1H NMR (400MHz, CDCl3) δ7.35–7.26(m,18H),7.15–7.10(m,2H),5.14(d,J=3.8Hz,1H),4.96(d,J=10.8Hz ,1H),4.83(d,J=10.7,1H),4.82(d,J=10.8Hz,1H),4.70(s,2H),4.60(d,J=12.1Hz,1H),4.47(d,J=10. 4Hz,1H),4.45(d,J=12.0Hz,1H),4.48–4.39(m,1H),3.96(t,J=9.4Hz,1H),3.89–3.84(m,1H),3.76(dd ,J=10.8,3.1Hz,1H),3.71(t,J=9.6Hz,1H),3.64(dd,J=9.8,3.8Hz,1H),3.60(dd,J=10.8,2.1Hz,1H). 13 CNMR(101MHz, CDCl3)δ138.71,138.08,137.80,137.72,128.61,128.57,128.55,128.22,128.12,128 .07,128.04,127.98,127.80,99.57,81.32,79.02,77.04,75.91,75.43,73.68,73.51,72.01,67.91. 19 F NMR(376MHz,CDCl3)δ-72.83.HRMS(ESI)m / z Calcd forC 37 H 36 F6O6Na + [M+Na] + :713.2308,found:713.2304; m / z Calcd for C 37 H 40 F6NO6 + [M+NH4] + :708.2754,found:708.2756.

[0080] Embodiment 39

[0081] Using F1, G3, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D5 (152.1 mg) was obtained with a yield of 81% and β configuration. D5 is a known compound, a colorless oil (R f =0.5, petroleum ether / ethyl acetate=5:1). 1H NMR (400MHz, CDCl3) δ7.37–7.22(m,28H),7.21–7.14(m,2H),5.05(t,J=8.1H z,1H),4.97(d,J=11.0Hz,1H),4.87–4.72(m,5H),4.64(dd,J=11.8,3.2Hz,2H ),4.60–4.49(m,5H),4.39(d,J=8.0Hz,1H),4.09(d,J=10.6Hz,1H),3.96(t,J =9.3Hz,1H),3.79–3.59(m,6H),3.56–3.41(m,3H),3.34(s,3H),1.86(s,3H). 13 C NMR (101MHz, CDCl3) δ169.26,138.90,138.32,138.20,138.16,137.88,128.51,128. 41,128.22,128.18,128.09,128.02,127.96,127.94,127.91,127.88,127.82,127.79 ,127.73,127.64,127.59,101.02,98.07,83.09,82.08,79.89,78.09,77.80,75.73,75.42,75.10,75.06,74.92,73.49,73.47,72.99,69.77,68.85,67.96,55.13,21.00.

[0082] Embodiment 40

[0083] Using F4, G3, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D6 (116.7 mg) was obtained with a yield of 75% and α:β=1.5:1. D6 is a known compound, and its NMR spectrum is consistent with that reported in the literature (Org. Lett. 2024, 26, 2478-2482).

[0084] Embodiment 41

[0085] Using F6, G4, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D7 (141 mg) was obtained with a yield of 95% and β configuration. D7 is an unknown compound, a colorless oil (R f =0.13, petroleum ether / ethyl acetate=2:1). 1H NMR(400MHz, CDCl3)δ9.14(s,1H),7.58(d,J=1.5Hz,1H),7.38–7.26(m,15H),6.30(t,J=6.6Hz,1H),5.32 (dd,J=10.1,7.9Hz,1H),4.87(d,J=11.3Hz,1H),4.69(d,J=12.3Hz,1H),4.54(d,J=12.2,1H),4.53(d,J=1 0.9Hz,1H),4.45(s,2H),4.34(d,J=8.0Hz,1H),4.23(dd,J=10.7,2.0Hz,1H),4.16–4.10(m,1H),4.02–3.9 9(m,1H),3.97(d,J=2.9Hz,1H),3.63–3.50(m,5H),2.32–2.22(m,2H),2.04(s,3H),1.77(d,J=1.2Hz,3H). 13 C NMR (101MHz, CDCl3) δ169.93,164.15,150.62,138.08,137.81,137.65,1 35.92,128.57,128.55,128.45,128.38,128.07,128.03,127.99,127.96, 127.63,111.86,101.19,84.36,82.75,79.68,74.96,74.04,73.64,72.8 2,72.18,71.47,68.63,68.38,61.00,37.36,21.04,12.17.HRMS(ESI)m / z Calcd for C 39 H 43 N5O 10 Na + [M+Na] + :764.2902,found:764.2904.

[0086] Embodiment 42

[0087] Using F6, G5, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D8 (157.9 mg) was obtained with a yield of 95% and β configuration. D8 is an unknown compound, a colorless oil (R f =0.33, petroleum ether / ethyl acetate=2:1). 1H NMR(400MHz, CDCl3)δ8.38(s,1H),7.59(d,J=1.6Hz,1H),7.40–7.23(m,15H),6.42(dd,J=8.3,6.1Hz,1H),5.3 3(dd,J=10.1,8.0Hz,1H),4.87(d,J=11.3Hz,1H),4.70(d,J=12.3Hz,1H),4.56–4.50(m,2H),4.44(s,2H),4.3 2(d,J=8.0Hz,1H),4.30–4.25(m,1H),4.15(dd,J=10.4,2.1Hz,1H),4.02–3.95(m,2H),3.64–3.51(m,4H),3.4 8(dd,J=10.4,2.0Hz,1H),2.13–2.06(m,2H),2.01(s,3H),1.75(s,3H),0.87(s,9H),0.05(s,3H),0.04(s,3H). 13 C NMR (101MHz, CDCl3) δ169.59,163.89,150.60,138.17,137.90,137.71,136.44, 128.61,128.58,128.47,128.41,128.12,128.07,128.01,127.97,127.67,111.8 2,101.35,86.44,84.95,79.78,75.01,74.05,73.72,73.52,72.90,72.13,71.4 7,69.42,68.43,40.80,25.84,21.01,18.13,12.20,-4.62,-4.75.HRMS(ESI)m / z Calcd for C 45 H 58 N2O 11 SiNa + [M+Na] + :853.3702,found:853.3701.

[0088] Embodiment 43

[0089] Using F6, G6, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D9 (185.7 mg) was obtained with a yield of 77% and β configuration. D9 is an unknown compound, a colorless oil (R f =0.4, dichloromethane / methanol=20:1). 1H NMR(400MHz,CDCl3)δ7.74(d,J=7.7Hz,2H),7.58(d,J=8.9Hz,2H),7.40–7.18(m,19H),6.12–6.00(m,2H),5.80(brs,1H),5.60(brs,1H),5.11(t,J=8.9Hz,1H),4.78(d,J=11.1Hz,1H),4.56(d,J=11.7Hz,1H),4.53(d,J=11.7Hz,1H),4.45–4.30(m,7H),4.25(d,J=8.1Hz,1H),4.21–4.12(m,2H),3.97(d,J=3.2Hz,1H),3.53(s,2H),3.52–3.39(m,3H),3.27–3.13(m,2H),3.00–2.85(m,2H),2.80–2.66(m,1H),2.62(s,3H),2.54(s,3H),2.09(s,3H),1.99(s,3H),1.94–1.83(m,2H),1.82–1.45(m,6H),1.44–1.38(m,6H). 13 C NMR(101MHz,CDCl3)δ170.20,169.67,158.40,156.01,155.87,143.96,143.83,141.24,138.26,137.46,133.75,132.29,128.83,128.53,128.44,128.24,128.05,128.02,127.84,127.65,127.58,127.05,125.19,124.42,119.92,117.18,101.48,86.17,79.36,77.36,75.04,73.56,73.40,72.68,72.16,71.64,68.77,67.96,66.87,56.47,52.24,47.67,47.19,43.22,40.30,29.78,28.58,28.56,27.00,24.60,20.86,19.39,18.03,12.51.HRMS(ESI)m / z Calcd for C 68 H 79 N5O 13 SNa + [M+Na] + :1228.5287,found:1228.5294;m / z Calcd for C 68 H 80 N5O13 S + [M+H] + :1206.5468,found:1206.5491.

[0090] Embodiment 44

[0091] Using F9, G7, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D10 (142 mg) was obtained with a yield of 84% and β configuration. D10 is an unknown compound, a colorless oil (R f =0.3, petroleum ether / ethyl acetate=5:1). 1 H NMR (400MHz, CDCl3) δ7.40–7.24(m,25H),5.94–5.83(m,1H),5.33–5.26(m,1H),5.21–5.14(m,2H),4.96(d,J=11.5Hz,1H),4.85 (d,J=3.7Hz,1H),4.83(d,J=12.1Hz,1H),4.78(d,J=12.0Hz,1H),4.70(d,J=11.7Hz,1H),4.65(d,J=12.1Hz,1H),4.64(d,J=12. 3Hz,1H),4.60(d,J=12.3Hz,1H),4.59(d,J=12.3Hz,1H),4.54(d,J=11.4Hz,1H),4.53(d,J=11.4Hz,1H),4.26(d,J=5.0Hz,1H), 4.14–3.92(m,7H),3.78(dd,J=9.2,5.5Hz,1H),3.74–3.69(m,1H),3.59–3.51(m,2H),3.34(dd,J=11.9,2.7Hz,1H),1.98(s,3H). 13 C NMR (101MHz, CDCl3) δ169.46,139.03,138.71,138.15,138.11,133.99,128.47, 128.44,128.39,128.34,128.31,128.10,127.92,127.81,127.70,127.65,127.5 3,127.50,118.23,99.99,96.19,79.12,76.59,76.04,75.21,74.85,73.40,73.3 4,71.54,71.48,71.33,70.23,68.87,68.18,66.58,61.11,21.11.HRMS(ESI)m / z Calcd forC51 H 56 O 11 Na + [M+Na] + :867.3715,found:867.3711; m / z Calcd for C 51 H 60 NO 11 + [M+NH4] + :862.4161,found:862.4163.

[0092] Embodiment 45

[0093] Using F8, G8, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D11 (86.1 mg) was obtained with a yield of 95% and β configuration. D11 is an unknown compound, a colorless oil (R f =0.5, petroleum ether / ethyl acetate=5:1). 1 H NMR (400MHz, CDCl3) δ7.39–7.22(m,10H),5.34(t,J=8.3Hz,1H),4.97(d,J=1 1.8Hz,1H),4.67(d,J=11.6Hz,2H),4.54(d,J=12.2Hz,1H),4.30(d,J=7.9Hz, 1H),3.96–3.87(m,1H),3.63–3.58(m,1H),3.57–3.45(m,3H),2.32–2.15(m,2 H),2.05(s,3H),1.93–1.87(m,1H),1.86–1.63(m,2H),1.22(d,J=5.0Hz,3H). 13 C NMR (101MHz, CDCl3) δ169.77,138.45,138.11,128.53,128.26,127.87,127.67,127.59,101.51,8 0.71,75.24,74.52,72.16,71.44,70.70,68.54,67.56,28.43,21.12,16.97,14.94.HRMS(ESI)m / z Calcd for C 27 H 32 O6Na + [M+Na] + :475.2091,found:475.2089; m / z Calcd for C 27 H 36 NO6+ [M+NH4] + :470.2537,found:470.2546.

[0094] Embodiment 46

[0095] Using F1, G9, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D12 (119.1 mg) was obtained with a yield of 95% and β configuration. D12 is a known compound, a colorless oil (R f =0.68, petroleum ether / ethyl acetate=5:1). 1 H NMR (400MHz, CDCl3) δ7.35–7.24(m,13H),7.22–7.18(m,2H),4.94(dd,J=9.3,8.0Hz,1H),4.79(d,J=10.69,1H),4.78(d,J=11.4Hz,1H),4.69– 4.53(m,5H),3.77–3.57(m,4H),3.51–3.45(m,1H),2.16–2.08(m,3H), 1.96(s,3H),1.87–1.83(m,1H),1.83–1.80(m,2H),1.74–1.54(m,10H). 13 C NMR (101MHz, CDCl3) δ169.44,138.49,138.42,138.13,128.54,128.42,128.14,128.02,127.95,127.81 ,127.72,127.61,94.09,83.45,78.45,75.07,75.04,73.67,73.53,69.39,42.61,36.34,30.75,21.18.

[0096] Embodiment 47

[0097] Using F5, G10, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D13 (157.1 mg) was obtained with a yield of 78% and an α:β=1:1 configuration. D13 is an unknown compound, a colorless oil (R f =0.3, petroleum ether / ethyl acetate=2:1). 11H NMR (400 MHz, CDCl3) δ 8.94 (s, 0.7H), 8.89 (s, 0.3H), 8.64 (s, 0.3H), 7.52–7.46 (m, 2H), 7.44–7.09 (m, 33H), 6.90 (d, J = 1.5 Hz, 0.7H), 6.48 (dd, J = 9.4, 5.6 Hz, 0.3H), 6.30 (dd, J = 9.5, 5.3 Hz, 0.7H), 4.90–4.84 (m, 1H), 4.80 (s, 0.7H), 4.78–4.73 (m, 1.3H), 4.70–4.49 (m, 4H), 4.48–4.38 (m, 2H), 4.21–4.17 (m, 1.3H), 4.08 (t, J = 9.3 Hz, 0.7H), 3.89–3.77 (m, 1H), 3.75–3.63 (m, 0.7H), 3.54–3.26 (m, 5.3H), 3.03–3.96 (m, 1H), 1.87–1.76 (m, 1H), 1.49 (s, 3H), 1.13–1.02 (m, 1H). 13 13C NMR (101 MHz, CDCl3) δ 163.72, 150.65, 150.23, 144.35, 143.99, 138.58, 138.20, 138.01, 135.01, 128.97, 128.85, 128.57, 128.51, 128.45, 128.42, 128.39, 128.20, 128.13, 128.06, 128.03, 127.93, 127.87, 127.81, 127.79, 127.67, 127.59, 127.55, 111.28, 110.89, 100.00, 97.35, 88.20, 85.08, 84.79, 79.17, 77.36, 75.62, 75.43, 75.16, 74.97, 74.67, 74.58, 73.69, 73.17, 72.81, 72.63, 72.50, 72.39, 68.53, 66.87, 39.53, 25.03, 12.79, 12.05. HRMS (ESI) m / z Calcd for C 63 H 62 N2O 10 Na + [M+Na] + : 1029.4297, found: 1029.4304.

[0098] Example 48

[0099] Using F4, G11, and H1 as raw materials, according to the synthesis steps of method B, 0.2 mmol was added, and finally the product D14 (100.2 mg) was obtained with a yield of 64% and an α:β=2.8:1 configuration. D14 is an unknown compound, a colorless oil (R f =0.12, petroleum ether / ethyl acetate=5:1). 1 H NMR (400MHz, CDCl3) δ7.43–7.36(m,2H),7.34–7.24(m,16H),7.15(dd,J=7.3,2.2Hz,2H),5. 82(d,J=3.7Hz,1H),5.24(d,J=3.6Hz,1H),4.98(d,J=10.7Hz,1H),4.89–4.79(m,2H),4.79– 4.74(m,2H),4.69(d,J=11.9Hz,1H),4.59–4.40(m,3H),4.30–4.22(m,2H),4.12–4.00(m,3H ),4.00–3.92(m,2H),3.71–3.57(m,4H),1.57(s,3H),1.43(s,3H),1.37(s,3H),1.31(s,3H). 13 C NMR (101MHz, CDCl3) δ138.92,138.73,138.53,138.00,128.44,128.37,128.32 ,128.13,127.93,127.89,127.77,127.72,127.65,127.57,127.54,113.34,10 9.63,104.51,94.56,81.78,79.35,78.46,77.56,75.74,75.57,74.75,74.16, 73.53,71.91,70.66,68.65,65.82,27.03,26.93,26.50,24.98.HRMS(ESI)m / z Calcd for C 46 H 54 O 11 Na + [M+Na] + :805.3558,found:805.3559; m / z Calcd for C 46 H 58 NO 11 [M+NH4] + :800.4004,found:800.4003.

[0100] Embodiment 49

[0101] Using F13, G12, and H1 as raw materials, according to the synthesis steps of method B, 0.2 mmol was added, and finally the product D15 (141.4 mg) was obtained with a yield of 95% and an α:β=4:1 configuration. D15 is an unknown compound, a white solid (R f =0.1, petroleum ether / ethyl acetate = 5:1). The NMR data of the α-configuration product are as follows: 1 H NMR (400MHz, CDCl3) δ7.71(dd,J=7.6,2.3Hz,2H),7.57(t,J=7.3Hz,2H),7.37–7.19(m,19H),6.52(d,J=9.1Hz,1H),4.97(d,J =4.0Hz,1H),4.68(d,J=12.2Hz,1H),4.59–4.34(m,8H),4.30–4.11(m,4H),3.94–3.82(m,3H),3.69(s,3H),3.48–3.37(m,2H). 13 C NMR (101MHz, CDCl3) δ171.02,156.45,144.13,143.82,141.29,141.23,138.08,13 7.84,137.75,128.46,128.32,128.29,127.94,127.79,127.76,127.70,127.67,1 27.63,127.08,127.04,125.39,125.18,119.95,119.92,101.21,82.53,78.39,75 .59,73.54,72.59,72.49,70.01,68.06,67.05,54.45,52.55,47.10.HRMS(ESI)m / z Calcd for C 45 H 45 NO9 + [M+Na] + :766.2987,found:766.2986.

[0102] Embodiment 50

[0103] Using F6, G13, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D16 (88.5 mg) was obtained with a yield of 74% and β configuration. D16 is an unknown compound, a colorless oil (R f =0.4, petroleum ether / ethyl acetate=1:1). 1H NMR (400MHz, CDCl3) δ8.75(d,J=4.9,1H),8.09(d,J=7.7Hz,1H),7.78(t,J=7.8,1H),7.43(dd,J=7.8 ,4.7,1H),7.39–7.25(m,15H),5.88(d,J=8.2Hz,1H),5.68(dd,J=10.1,8.2Hz,1H),4.96(d,J=11.4H z,1H),4.70(d,J=12.2Hz,1H),4.63(d,J=11.5Hz,1H),4.56(d,J=12.2Hz,1H),4.47(d,J=11.7Hz,1H ),4.40(d,J=11.6Hz,1H),4.06(d,J=2.3Hz,1H),3.87–3.80(m,1H),3.72–3.59(m,3H),1.94(s,3H). 13 CNMR(101MHz, CDCl3)δ169.69,162.84,150.28,146.68,138.21,137.68,137.64,137.24,128.49,128.46,128.41,128.29,128.24,128.01,12 7.99,127.92,127.89,127.72,127.57,127.34,125.96,93.64,79.84, 74.77,74.56,73.57,72.48,72.22,70.38,67.86,20.86.HRMS(ESI)m / z Calcd for C 35 H 35 NO8Na + [M+Na] + :620.2255,found:620.2259.

[0104] Embodiment 51

[0105] Using F9, G14, and H1 as raw materials, according to the synthesis steps of method A, 0.2 mmol was added, and finally the product D17 (143.8 mg) was obtained with a yield of 95% and β configuration. D17 is an unknown compound, a white solid (R f =0.12, petroleum ether / ethyl acetate=2:1). 1H NMR (400MHz, CDCl3) δ7.37–7.28(m,10H),5.69(d,J=4.7Hz,1H),5.29(dd,J=6.7,4.7Hz,1H),4.67(d,J=12.2Hz,1H),4.64–4 .58(m,3H),4.11(dd,J=11.8,6.5Hz,1H),3.81–3.76(m,1H),3.71(dd,J=6.6,3.1Hz,1H),3.55(dd,J=11.8,2.9Hz,1H),2.95 –2.78(m,3H),2.48–2.38(m,1H),2.37–2.21(m,6H),2.21–2.17(m,1H),2.17–2.13(m,1H),2.13–2.09(m,1H),2.04(s,3H),2 .02–1.91(m,4H),1.87–1.77(m,2H),1.65–1.54(m,1H),1.39(s,3H),1.36–1.20(m,4H),1.05(s,3H),0.82(d,J=6.5Hz,3H). 13 C NMR (101MHz, CDCl3) δ211.92,209.15,208.74,172.53,169.39,137.92,128.45,1 28.42,127.84,127.81,127.63,91.74,75.37,71.86,71.36,71.31,69.12,61.84, 56.92,51.73,49.00,46.85,45.67,45.53,45.01,42.82,38.65,36.52,36.03,35. 47,35.29,31.64,30.16,27.52,25.15,21.92,20.92,18.64,11.88.HRMS(ESI)m / z Calcd forC 45 H 56 O 10 Na + [M+Na] + :779.3766,found:779.3767.

[0106] Embodiment 52

[0107] Using F9, G15, and H1 as raw materials, according to the synthesis steps of method A, 0.1 mmol was added, and finally the product D18 (127.4 mg) was obtained with a yield of 75% and β configuration. D18 is an unknown compound, a white solid (R f=0.4, dichloromethane / methanol=20:1). 1 H NMR (400MHz, DMSO-d6) δ8.55(s,1H),8.24(t,J=6.3Hz,1H),8.14(d,J=8.0H z,1H),7.99(d,J=7.7Hz,1H),7.70(d,J=7.9Hz,1H),7.39–7.23(m,17H),7. 21–7.15(m,9H),7.15–7.07(m,3H),6.83(d,J=8.1Hz,2H),6.35(brs,1H),5 .59(d,J=7.4Hz,1H),5.14(dd,J=9.2,7.3Hz,1H),4.70–4.43(m,5H),4.33– 4.17(m,3H),4.07(d,J=11.1Hz,1H),3.98–3.74(m,4H),3.63–3.56(m,1H), 3.06–2.96(m,2H),2.95(s,3H),2.81–2.69(m,1H),2.66–2.56(m,1H),2.48 (s,3H),2.43(s,3H),2.41–2.29(m,3H),2.02–1.98(m,6H),1.92–1.82(m,1 H),1.80–1.68(m,1H),1.64–1.53(m,1H),1.42–1.33(m,27H),1.24(s,9H). 13 C NMR (101MHz, DMSO-d6) δ171.94,171.59,171.14,170.88,169.56,169.34,168.58,157.54,156.09,155. 22,153.48,144.92,138.48,138.36,137.37,132.22,131.52,129.73,128.57,128.29,128.25,127.70,1 27.60,127.56,127.54,127.44,126.41,124.38,123.37,116.35,92.59,86.35,80.15,78.49,77.61,76 .95,71.89,70.59,70.52,69.29,28.60,28.36,28.18,27.73,20.64,19.04,17.69,12.35.HRMS(ESI)m / z Calcd for C 92 H 115 N9O 20 SNa + [M+Na] +:1720.7871,found:1720.7904.

[0108] Embodiment 53

[0109] Using F6, G16, and H1 as raw materials, according to the synthesis steps of method A, 0.1 mmol was added, and finally the product D19 (108.6 mg) was obtained with a yield of 74% and β configuration. D19 is an unknown compound, white solid (R f =0.5, dichloromethane / methanol=15:1). 1 H NMR (400MHz, DMSO-d6) δ8.94(d,J=7.9Hz,1H),8.46(s,1H),8.17(d,J=8.1Hz,1H ),8.10–8.02(m,2H),8.02–7.80(m,7H),7.66–7.56(m,2H),7.38–7.25(m,15H), 7.23–7.09(m,12H),6.97(s,1H),5.66(d,J=8.3Hz,1H),5.16(t,J=9.2Hz,1H),4 .98–4.89(m,1H),4.80(d,J=11.3Hz,1H),4.71(d,J=12.2Hz,1H),4.68–4.60(m,1 H),4.53(d,J=11.7Hz,2H),4.47(d,J=12.0Hz,1H),4.43–4.36(m,3H),4.35–4.2 8(m,1H),4.18–4.06(m,3H),3.97(t,J=6.3Hz,1H),3.88(d,J=10.3Hz,1H),3.81– 3.64(m,2H),3.58–3.45(m,4H),3.07–3.00(m,1H),2.95–2.77(m,3H),1.99–1.9 0(m,1H),1.88(s,3H),1.69–1.40(m,6H),1.31–1.14(m,4H),0.90–0.77(m,15H). 13C NMR(101MHz,DMSO-d6)δ173.58,171.64,171.05,170.63,170.30,169.21,168.96,168.54,166.38,138.54,138.31,138.02,13 7.93,137.50,134.25,132.03,131.08,129.16,128.77,128.24,128.16,128.04,127.97,127.77,127.64,127.54,127.51,127 .47,127.38,127.24,126.78,126.18,124.28,92.10,78.81,74.07,73.64,72.32,72.16,71.05,69.70,68.12,57.87,54.90,5 2.77,52.41,51.10,41.94,40.91,31.55,30.45,27.48,24.09,23.06,21.84,21.60,20.50,19.10,18.08,13.83.HRMS(ESI)m / z Calcd for C 82 H 99 N8O 17 + [M+H] + :1467.7123,found:1467.7129.

[0110] Embodiment 54

[0111] Using F1, G17, and H1 as raw materials, according to the synthesis steps of method A, 0.1 mmol was added, and finally the product D20 (104.8 mg) was obtained with a yield of 88% and β configuration. D20 is an unknown compound, a white solid (R f =0.15, dichloromethane / methanol=20:1). 11H NMR (400 MHz, DMSO-d6) δ 8.41 (d, J = 6.9 Hz, 1H), 8.19 (t, J = 5.9 Hz, 1H), 7.95 (d, J = 7.6 Hz, 1H), 7.93–7.82 (m, 5H), 7.78 (d, J = 7.4 Hz, 1H), 7.37–7.23 (m, 13H), 7.22–7.14 (m, 4H), 6.95 (s, 1H), 6.69 (s, 1H), 5.71 (d, J = 8.3 Hz, 1H), 4.88–4.79 (m, 2H), 4.72 (t, J = 11.7 Hz, 2H), 4.61 (d, J = 11.4 Hz, 1H), 4.55–4.40 (m, 3H), 4.31–4.19 (m, 2H), 4.19–4.11 (m, 2H), 3.91 (t, J = 9.3 Hz, 1H), 3.81–3.76 (m, 1H), 3.73 (d, J = 5.7 Hz, 2H), 3.68–3.55 (m, 3H), 2.38 (t, J = 8.3 Hz, 2H), 2.04 (t, J = 7.7 Hz, 2H), 1.95 (s, 3H), 1.94–1.88 (m, 1H), 1.86–1.56 (m, 4H), 1.52–1.41 (m, 5H), 1.20 (d, J = 7.1 Hz, 3H), 0.88 (d, J = 6.5 Hz, 3H), 0.83 (d, J = 6.5 Hz, 3H). 13 13C NMR (101 MHz, DMSO-d6) δ 174.05, 173.89, 171.85, 171.31, 170.97, 170.85, 169.15, 169.04, 167.38, 138.20, 137.97, 134.31, 131.92, 128.24, 127.88, 127.70, 127.59, 127.49, 123.00, 81.40, 77.41, 74.67, 74.22, 74.08, 72.23, 71.71, 51.18, 48.05, 47.77, 31.47, 27.12, 24.12, 23.07, 21.41, 20.45, 18.10, 14.98. HRMS (ESI) m / z Calcd for C 61 H 74 N8O 17 Na + [M+Na] + : 1213.5064, found: 1213.5071.

[0112] Example 55

[0113] Using F5, G18, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D21 (113.7 mg) was obtained with a yield of 71% and α configuration. D21 is a known compound, a colorless oil (R f =0.3, petroleum ether / ethyl acetate=5:1). 1 H NMR (400MHz, CDCl3) δ7.37–7.22(m,28H),7.19–7.14(m,2H),5.78(dd,J=6.2,2.0Hz,1H),5 .02(d,J=8.2Hz,2H),4.96(d,J=8.5Hz,2H),4.86(d,J=10.8Hz,1H),4.66(s,2H),4.60(d,J= 12.0Hz,1H),4.54–4.47(m,3H),4.44(d,J=12.1Hz,1H),4.04(t,J=9.7Hz,1H),3.90(dd,J=1 0.0,4.6,1H),3.82(dd,J=9.5,3.1Hz,1H),3.75–3.66(m,2H),3.56(dd,J=11.0,1.8Hz,1H). 13 C NMR (101MHz, CDCl3) δ138.35,138.22,138.20,137.81,135.74,135.67,135 .60,128.60,128.56,128.40,128.35,128.31,127.98,127.93,127.89,127. 82,127.78,127.69,127.66,127.53,96.37,96.31,78.87,75.16,74.46,74.37,74.10,73.93,73.41,72.73,72.23,69.47,69.45,69.42,69.39,68.68. 31 P NMR (162MHz,CDCl3)δ-2.63.

[0114] Embodiment 56

[0115] Using F7, G18, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D22 (137.8 mg) was obtained with a yield of 86% and α configuration. D22 is a known compound, a colorless oil (R f =0.3, petroleum ether / ethyl acetate=5:1). 1H NMR (400MHz, CDCl3) δ7.38–7.22(m,28H),7.13(dd,J=7.3,2.3Hz,2H),5.97(dd,J=6.8,3.2H z,1H),5.09–5.00(m,4H),4.92(d,J=10.9Hz,1H),4.82(d,J=10.8Hz,1H),4.78(d,J=11.4Hz ,2H),4.67(d,J=11.3Hz,1H),4.54(d,J=12.1Hz,1H),4.48(d,J=10.8Hz,1H),4.41(d,J=12. 1Hz,1H),3.95–3.87(m,2H),3.71(t,J=9.6Hz,1H),3.67–3.61(m,2H),3.47(d,J=10.8,1H). 13 C NMR (101MHz, CDCl3) δ138.59,138.17,137.85,137.68,135.95,135.87,128.59,128.54,128.51,128.48,128.41,128.22,128.02,128.00,127. 96,127.90,127.83,127.80,127.76,95.77,95.71,81.20,79.36,79.29 ,75.74,75.21,73.54,73.09,72.58,69.40,69.35,69.21,69.16,67.96. 31 P NMR (162MHz,CDCl3)δ-2.20.

[0116] Embodiment 57

[0117] Using F12, G18, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D23 (185 mg) was obtained with a yield of 75% and α configuration. D23 is a known compound, a colorless oil (R f =0.2, petroleum ether / ethyl acetate=5:1). 1H NMR (400MHz, CDCl3) δ7.31–7.17(m,43H),7.12–7.07(m,2H),5.98(dd,J=6.7,3.3Hz,1H),5.68(d,J=3. 6Hz,1H),5.09–5.01(m,4H),4.95(d,J=11.7Hz,1H),4.89(d,J=10.8Hz,1H),4.81–4.69(m,4H),4.61–4 .48(m,4H),4.45–4.39(m,3H),4.27(d,J=12.1Hz,1H),4.16–4.09(m,1H),4.05–3.98(m,2H),3.90(t,J =9.3Hz,1H),3.78(dd,J=11.3,3.2Hz,1H),3.74–3.61(m,3H),3.55–3.45(m,3H),3.39(d,J=10.8,1H). 13 C NMR (101MHz, CDCl3) δ138.84,138.79,138.55,138.21,138.02,137.99,137.46,135.98,135.93,135.91,135.86, 128.63,128.57,128.52,128.49,128.45,128.43,128.39,128.36,128.15,127.99,127.96,127.90,127.88,127. 86,127.79,127.73,127.70,127.63,127.58,127.47,127.29,126.79,97.16,95.39,95.33,82.06,81.27,79.47,77.74,75.66,75.10,74.46,73.59,73.40,73.35,73.07,72.28,71.83,71.17,69.43,69.38,69.23,68.44,68.23. 31 P NMR (162MHz,CDCl3)δ-2.02.

[0118] Embodiment 58

[0119] Using F5, G19, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D24 (143.5 mg) was obtained with a yield of 62% and α configuration. D24 is an unknown compound, a colorless oil (R f =0.25, petroleum ether / ethyl acetate=2:1). 1H NMR (400MHz, CDCl3) δ7.36–7.21(m,38H),7.18–7.13(m,2H),5.83–5.78(m,1H),5.0 5(d,J=8.2Hz,1H),4.99–4.93(m,2H),4.89–4.76(m,3H),4.70(dd,J=12.2,4.5Hz,1 H),4.67(s,2H),4.61–4.35(m,8H),4.22(dd,J=6.6,3.2Hz,1H),4.19–4.04(m,2H), 3.99–3.65(m,6H),3.64–3.53(m,1H),3.49–3.39(m,2H),3.29(s,3H).HRMS(ESI)m / z Calcd for C 69 H 73 O 14 PNa + [M+Na] + :1179.4630,found:1179.4638.

[0120] Embodiment 59

[0121] Using F13, G20, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D25 (107.7 mg) was obtained with a yield of 74% and an α:β=1:1.5 configuration. D25 is an unknown compound, a colorless oil (R f =0.2, petroleum ether / ethyl acetate=5:1). 1 H NMR (400MHz, CDCl3) δ7.38–7.26(m,13H),7.22–7.17(m,2H),6.31(d,J=9.2Hz,0.6H),5.69( d,J=8.7Hz,0.4H),5.45(dd,J=9.1,5.6Hz,0.6H,β),5.33(dd,J=8.7,2.3Hz,0.4H,α),4.78–4 .37(m,6H,OBn),4.37–4.28(m,2H),4.25–4.19(m,1H),4.16–4.03(m,2H),4.01–3.87(m,2H), 3.79–3.69(m,1H),3.64(dd,J=10.4,2.6Hz,0.4H),3.47–3.36(m,1.6H),1.55–1.28(m,12H). 13C NMR (101MHz, CDCl3) δ137.88,137.59,137.56,137.34,137.18,136.89,128.89,128.68,128.66,128.61,128.5 7,128.40,128.36,128.21,128.14,128.11,128.07,127.90,127.66,109.31,109.24,109.21,101.12,101.06, 87.95,83.61,82.08,81.66,80.75,77.66,77.36,76.26,73.94,73.67,73.07,72.62,72.46,72.24,70.90,70. 77,70.26,70.17,70.02,69.94,69.83,69.25,68.78,61.49,26.66,26.02,25.37,25.30,24.24.HRMS(ESI)m / z Calcd for C 37 H 45 NO 12 SNa + [M+Na] + :750.2555,found:750.2557.

[0122] Embodiment 60

[0123] Using F13, G21, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D26 (131.7 mg) was obtained with a yield of 84% and an α:β=1:1 configuration. D26 is an unknown compound, a colorless oil (R f =0.26, petroleum ether / ethyl acetate=5:1). 1 H NMR(400MHz, CDCl3) δ7.86(d,J=8.7Hz,1H),7.65(d,J=8.7Hz,1H),7.38–7.21(m ,15H),7.20–7.04(m,6H),6.73(s,1H),6.35(d,J=9.1Hz,0.5H),5.65(d,J=9.2H z,0.5H),5.50(dd,J=9.1,5.5Hz,0.5H,H1-β),5.30(dd,J=9.3,2.4Hz,0.5H,H1- α),4.74–4.28(m,6H),4.11–3.89(m,3H),3.42–3.25(m,2H),2.39–2.31(m,6H). 13C NMR (101MHz, CDCl3) δ145.27,142.38,142.17,141.74,140.59,139.78,139.76,137.76,137.49,137.45,137.33,13 7.11,136.93,129.82,129.80,128.86,128.83,128.80,128.65,128.60,128.53,128.37,128.30,128.18,128.15,12 8.09,128.05,128.00,127.95,127.88,127.70,127.63,125.89,125.87,125.26,125.23,106.31,87.74,83.34,81.8 2,81.42,81.14,77.69,76.12,73.76,73.58,72.95,72.49,72.42,72.29,69.86,68.81,21.42,21.40.HRMS(ESI)m / z Calcd for C 43 H 40 F3N3O6SNa + [M+Na] + :806.2482,found:806.2481.

[0124] Embodiment 61

[0125] Using F13, G22, and H1 as raw materials, according to the synthesis steps of method B, 0.2 mmol was added, and finally the product D27 (87.8 mg) was obtained with a yield of 63% and β configuration. D27 is an unknown compound, white solid (R f =0.3, petroleum ether / ethyl acetate=2:1). 1H NMR (400MHz, CDCl3) δ7.36–7.27(m,18H),7.24–7.20(m,2H),6.95(d,J=9.2Hz,1H),5.87(dd,J=9.2,5.5Hz,1H) ,5.66(d,J=7.9Hz,1H),5.13–5.01(m,2H),4.67(d,J=11.9Hz,1H),4.61(d,J=11.9Hz,1H),4.56(d,J=11.7Hz,1H ),4.51(d,J=11.4Hz,1H),4.50(d,J=11.8Hz,1H),4.44(d,J=12.0Hz,1H),4.36–4.28(m,1H),4.26–4.21(m,1H), 4.05(t,J=5.3Hz,1H),4.01–3.97(m,1H),3.70(s,3H),3.49–3.36(m,2H),2.30–2.10(m,3H),2.03–1.92(m,1H). 13 C NMR(101MHz,MeOD)δ174.63,174.00,158.48,139.41,139.15,139.06,138.08,129.53,129.51,129.46,129.42,129.27,129.20,129.0 2,128.86,128.81,128.73,82.29,80.36,79.30,77.86,74.40,74.01,73.60,71.22,67.67,54.84,52.75,33.37,28.12.HRMS(ESI)m / z Calcd for C 40 H 44 N2O9Na + [M+Na] + :719.2939,found:719.2939.

[0126] Embodiment 62

[0127] Using F13, G23, and H1 as raw materials, according to the synthetic steps of method B, 0.2 mmol was added, and finally the product D28 (75.6 mg) was obtained with a yield of 68% and an α:β=1:1 configuration. D28 is an unknown compound, a colorless oil (R f =0.3, petroleum ether / ethyl acetate=2:1). 1H NMR (400MHz, CDCl3) δ7.36–7.27(m,13H),7.25–7.21(m,2H),5.32-5.23(m, 1H),4.68(d,J=12.1Hz,1H),4.63(s,1H),4.58(d,J=11.5Hz,1H),4.57(d,J= 12.0Hz,1H),4.52(d,J=12.1Hz,1H),4.49–4.41(m,2H),4.26–4.21(m,1H), 4.11–4.01(m,4H),4.00–3.95(m,2H),3.51–3.39(m,2H),1.31–1.23(m,6H). 13 C NMR (101MHz, CDCl3) δ138.04,137.81,137.68,128.51,128.50,128.48,127.97,127.93,127.77,127.64,83.0 5,80.88,78.08,77.00,76.92,73.57,72.78,72.38,70.23,62.58,62.53,62.43,62.38,16.28,16.21,16.14. 31 P NMR(162MHz,CDCl3)δ6.72.HRMS(ESI)m / zCalcd for C 30 H 38 NO7PNa + [M+Na] + :578.2278,found:578.2280.

[0128] Embodiment 63

[0129] Using F14, G23, and H1 as raw materials, according to the synthesis steps of method B (reaction temperature is 65 degrees Celsius), 0.2mmol scale was added, and finally the product D29 (73mg) was obtained with a yield of 54% and an α:β=1.3:1 configuration. D29 is an unknown compound, a colorless oil (R f =0.2, petroleum ether / ethyl acetate=2:1). 1H NMR (400MHz, CDCl3) δ7.34–7.25(m,18H),7.17–7.12(m,2H),5.27-5.20(m,1H),4.89(d,J= 11.0Hz,1H),4.81(d,J=11.0Hz,1H),4.77(d,J=10.9Hz,1H),4.70(d,J=11.4Hz,1H),4.59(d ,J=11.4Hz,1H),4.58(d,J=12.0Hz,1H),4.50(d,J=10.9Hz,1H),4.46(d,J=12.1Hz,1H),4.1 4–3.98(m,4H),3.90–3.79(m,2H),3.78–3.70(m,2H),3.69–3.58(m,3H),1.31–1.19(m,6H). 13 C NMR (101MHz, CDCl3) δ138.55,138.31,138.03,137.54,128.60,128.52,128.50,128.47,128.15,128.11,128.08,128.06,127. 94,127.82,127.81,81.79,78.59,77.41,75.74,75.08,73.66,72.37,70.10,68.69,62.93,62.87,62.81,16.35,16.28,16.21. 31 P NMR(162MHz,CDCl3)δ7.16.HRMS(ESI)m / zCalcd for C 38 H 46 NO8PNa + [M+Na] + :698.2853,found:698.2855.

[0130] Embodiment 64

[0131] Using F13, G24, and H1 as raw materials, according to the synthetic steps of method C, 0.2 mmol was added, and finally the product D30 (85.5 mg) was obtained with a yield of 83% and an α:β=1:1 configuration. D30 is a known compound, a colorless oil (R f =0.22, petroleum ether / ethyl acetate=2:1). 1H NMR (400MHz, CDCl3) δ9.80 (s, 0.5H), 9.69 (s, 0.5H), 7.89 (d, J = 8.1Hz, 0.5H), 7 .69(d,J=8.2Hz,0.5H),7.43–7.15(m,15H),6.31(d,J=4.9Hz,0.5H),6.04(d,J =1.8Hz,0.5H),5.64(dd,J=8.2,2.0Hz,0.5H),5.16(dd,J=8.2,1.9Hz,0.5H),4 .89–4.74(m,1H),4.66–4.28(m,6.5H),4.12–3.91(m,2H),3.73–3.44(m,1.5H). 13 C NMR (101MHz, CDCl3) δ163.94,163.85,150.86,150.38,142.68,140.26,137.66,137.40,137.3 5,137.32,137.24,137.03,128.64,128.61,128.57,128.52,128.48,128.27,128.21,128.17, 128.09,128.06,128.04,127.97,127.83,127.72,127.65,101.56,101.10,88.44,84.97,81.78,81.35,78.98,77.80,76.77,74.17,73.90,73.69,73.60,73.07,72.25,71.73,69.58,67.94.

[0132] Embodiment 65

[0133] Using F13, G25, and H1 as raw materials, according to the synthetic steps of method C, 0.2 mmol was added, and finally the product D31 (88.5 mg) was obtained with a yield of 79% and β configuration. D31 is an unknown compound, a colorless oil (R f =0.17, petroleum ether / ethyl acetate=2:1). 1H NMR(400MHz, CDCl3)δ9.14(s,1H),8.84(s,1H),7.39–7.24(m,11H),7.24–7. 14(m,4H),6.32(d,J=5.6Hz,1H),4.65(d,J=11.9Hz,1H),4.62(d,J=12.2Hz,1 H),4.57(d,J=11.7Hz,1H),4.54–4.50(m,2H),4.49–4.41(m,3H),4.07(dd,J =4.8,3.0Hz,1H),3.58(dd,J=10.8,3.1Hz,1H),3.45(dd,J=10.8,2.8Hz,1H). 13 C NMR (101MHz, CDCl3) δ154.04,148.68,147.41,137.43,136.82,136.76,128.78,128.76,128.70,128.49,128 .33,128.14,127.95,127.78,124.98,86.00,83.76,77.75,77.56,74.16,73.73,73.47,69.65.HRMS(ESI)m / z Calcd for C 30 H 29 N3O8Na + [M+Na] + :582.1847,found:582.1848.

[0134] Embodiment 66

[0135] Using F7, G26, and H1 as raw materials, according to the synthetic steps of method C (reaction temperature is 65 degrees Celsius), 0.2 mmol scale was added, and finally the product D32 (105.1 mg) was obtained with a yield of 81% and an α:β=1:4 configuration. D32 is a known compound, a colorless oil (R f =0.3, petroleum ether / ethyl acetate = 2:1). α configuration: 11H NMR (400 MHz, CDCl3) δ 8.30 (s, 1H), 7.42 (d, J = 1.5 Hz, 1H), 7.39–7.24 (m, 18H), 7.01 (dd, J = 6.6, 2.8 Hz, 2H), 6.07 (d, J = 2.0 Hz, 1H), 4.64 (d, J = 12.2 Hz, 1H), 4.61–4.55 (m, 2H), 4.54–4.47 (m, 4H), 4.35 (d, J = 11.5 Hz, 1H), 4.21–4.10 (m, 2H), 4.07 (dd, J = 6.4, 2.8 Hz, 1H), 3.83–3.76 (m, 2H), 3.70 (dd, J = 4.0, 1.9 Hz, 1H), 1.84 (s, 3H). 13 13C NMR (101 MHz, CDCl3) δ 163.71, 149.74, 138.85, 138.27, 137.93, 137.80, 136.62, 128.64, 128.61, 128.56, 128.52, 128.44, 128.05, 128.02, 127.98, 127.94, 127.76, 127.73, 108.83, 75.10, 75.04, 73.72, 73.39, 73.27, 72.38, 72.01, 65.61, 12.38. β configuration: 1 1H NMR (400 MHz, CDCl3) δ 8.71 (s, 1H), 7.42–7.13 (m, 20H), 6.65 (s, 1H), 5.59 (d, J = 8.8 Hz, 1H), 4.97 (d, J = 11.4 Hz, 1H), 4.85–4.71 (m, 3H), 4.61 (d, J = 11.4 Hz, 1H), 4.56 (d, J = 12.0 Hz, 1H), 4.48 (d, J = 11.9 Hz, 1H), 4.42 (d, J = 11.9 Hz, 1H), 4.00 (d, J = 2.5 Hz, 1H), 3.86 (t, J = 9.1 Hz, 1H), 3.81–3.70 (m, 2H), 3.60–3.46 (m, 2H), 1.63 (s, 3H). 13C NMR (101MHz, CDCl3) δ163.44,150.62,138.71,137.98,137.64,137.34,128.93,128.65,128.57,128.55,128.43,128.16,128 .05,128.02,127.99,127.91,127.85,127.74,110.97,83.73,75.68,74.91,74.69,74.48,73.60,73.34,72.76,68.09,12.62.

[0136] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a glycoside substance mediated by metal catalysis nitrene, characterized in that: The following steps are involved: Under a protective atmosphere, sugar substances, nucleophilic reagents, activators, metal catalysts and additives are reacted in an organic solvent to generate glycoside products.

2. The method for preparing metal-catalyzed nitrene-mediated glycosides according to claim 1, characterized in that: The carbohydrate substance is selected from at least one of the substances represented by the general structural formula of Formula I: Wherein, X is a heteroatom or a heteroatom group, preferably S or -S=O; Ar is selected from substituted or unsubstituted aryl; preferably phenyl, alkyl or alkoxy substituted phenyl; more preferably phenyl, C1-C6 alkyl or C1-C6 alkoxy substituted phenyl; n is 0 or 1; The R1 is selected from or at least one of an alkyl group, m is an integer of 1-4; preferably, the R1 is at least selected from * -OBn; Further preferably, said R1 is selected from * -OBn, and selected from or at least one of C1-C3 alkyl groups; m is an integer of 2-4; Further preferably, the carbohydrate substance is selected from at least one of the following substances:

3. The method for preparing metal-catalyzed nitrene-mediated glycosides according to claim 1, characterized in that: The nucleophile is selected from at least one of a hydroxyl-containing nucleophile, a carboxyl-containing nucleophile, a phosphate-containing nucleophile, an amide-containing nucleophile or a pyrimidine-containing nucleophile; Preferably, the nucleophile is selected from Nu-H or At least one of the substances shown; wherein Nu is a nucleophilic group obtained by removing the hydrogen atom from a hydroxyl-containing nucleophile, a carboxyl-containing nucleophile, a phosphate-containing nucleophile, or an amide-containing nucleophile; R3 is hydrogen, nitro, or a C1-C3 alkyl group; preferably, R3 is selected from hydrogen, nitro, or methyl; Further preferably, the nucleophilic agent is selected from at least one of the following substances:

4. The method for preparing metal-catalyzed nitrene-mediated glycosides according to claim 1, characterized in that: The activator is selected from at least one of the substances represented by the general structural formula of formula III: Wherein, the R2 is selected from an alkyl group, a substituted or unsubstituted aryl group; preferably, the R2 is selected from a C1-C10 alkyl group, a phenyl group or a C1-C6 alkoxy-substituted phenyl group; further preferably, the R2 is selected from a C1-C6 alkyl group, a phenyl group or a C1-C3 alkoxy-substituted phenyl group; further preferably, the activator is selected from at least one of the following substances:

5. The method for preparing metal-catalyzed nitrene-mediated glycosides according to claim 1, characterized in that: The metal catalyst is selected from at least one of an iron catalyst, a ruthenium catalyst or an iridium catalyst; preferably, the metal catalyst is selected from at least one of iron phthalocyanine, ferric phthalocyanine chloride, ferrous iodide, dichlorobis(4-methylisopropylphenyl)ruthenium or dichloro(pentamethylcyclopentadienyl)iridium dimer; and / or, The additive is selected from at least one of 2,6-di-tert-butylpyridine hydrochloride, 2,4,6-tri-tert-butylpyridine hydrochloride, 2,6-di-tert-butylpyridine trifluoromethanesulfonate, D-camphorsulfonic acid, L-camphorsulfonic acid, p-toluenesulfonic acid, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, silver hexafluorophosphate or silver tetrafluoroborate; and / or, The organic solvent is selected from at least one of hexafluoroisopropanol, dichloromethane, toluene, tetrahydrofuran or acetonitrile.

6. The method for preparing metal-catalyzed nitrene-mediated glycosides according to claim 1, characterized in that: The molar ratio of the sugar substance to the nucleophile is (1-4.5): (1-1.5); and / or, The molar ratio of the sugar substance to the activator is (1-4.5): (1.5-4.5).

7. The method for preparing metal-catalyzed nitrene-mediated glycosides according to claim 1, characterized in that: The molar ratio of the sugar substance or the nucleophilic reagent to the metal catalyst is (1-4.5): (0.005-0.1); and / or, The molar ratio of the sugar substance or the nucleophilic reagent to the additive is (1-4.5): (0.05-0.1); and / or, The reaction temperature is 25°C to 65°C; and / or, The reaction time is 1 to 24 hours.

8. A glycoside substance prepared by the method according to any one of claims 1 to 7, characterized in that: The glycoside substance is selected from at least one of the substances represented by the general structural formula of Formula IV or Formula V: Wherein, n in the general structural formula of Formula IV or Formula V is independently 0 or 1; R1 in the general structural formula of Formula IV or Formula V is independently selected from or at least one of the alkyl groups, m is an integer of 1-4; preferably, the R1 is at least selected from *-OBn; further preferably, the R1 is selected from *-OBn and selected from or at least one of C1-C3 alkyl groups; m is an integer of 2-4; Nu in formula IV is selected from the nucleophilic group after the nucleophilic reagent removes the hydrogen atom; R3 in Formula V is hydrogen, nitro or C1-C3 alkyl; preferably, R3 is selected from hydrogen, nitro or methyl.

9. The glycoside substance according to claim 8, characterized in that: The Nu is selected from the following groups:

10. The glycoside substance according to claim 8, characterized in that: The glycoside substance is selected from at least one of the following substances:

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