Preparation method of 1-O-glycosyl carbamate compound

Abstract

The invention discloses a preparation method of a 1-O-glycosyl carbamate compound. The invention provides a preparation method of a 1-O-glycosyl carbamate compound, which comprises the following steps: (1) carrying out carbamic acid reaction on an amine compound and carbon dioxide in a solvent under an alkali condition; and (2) after the reaction in the step (1) is finished, carrying out glycosylation reaction with halogenated glycoside to obtain the corresponding 1-O-glycosyl carbamate compound. The preparation method provided by the invention has one or more advantages as follows: the reaction raw materials are easy to obtain, the operation is simple and convenient, the reaction effect is good, and the 1-O-glycosyl carbamate compound can be stereoscopically and specifically obtained.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, and more specifically to a method for preparing 1-O-glycosylcarbamate compounds. Background Technology

[0002] 1-O-glycosyl carbamates are a class of compounds formed by linking the nitrogen atom of an amino group to the oxygen atom at the 1-position of a sugar via a carbonyl group. These compounds can be considered glycosylated products of amines. The 1-O-glycosyl carbamate structure can be hydrolyzed in vivo by glycosidases, releasing the precursor amine. This modification can significantly improve the water solubility and bioavailability of amine drugs, thus giving these compounds broad application value in the fields of biomedicine and chemical biology.

[0003] Currently, there are three main reported methods for preparing 1-O-glycosylcarbamates. The first method uses 1-O-glycosyl-p-nitrophenyl carbonate as the glycosylation reagent (Bioorganic & Medicinal Chemistry 2017, 25, 5692-5708) and condenses it with various amines. The disadvantage of this method is that it requires the prior preparation of the glycosylation reagent, a 1-O-glycosyl-p-nitrophenyl carbonate compound. This reagent is unstable, difficult to store for long periods, and difficult to separate and purify. Furthermore, the product is a mixture of two isomers (α / β-) at the 1-position of the glycosyl group, making it difficult to control the stereoselectivity of the glycosylation reaction. The second method first converts the amino group to an isocyanate, and then condenses it with the glycosylation reagent to obtain 1-O-glycosylcarbamate (Carbohydrate Research). The first method (1998, 305, 341-349) is only applicable to primary amine substrates, requires the amine to be converted to isocyanate beforehand, and it is difficult to control the stereoselectivity of the glycosylation reaction. The third method uses glycosyl sulfoxide glycoside as a donor and Boc-protected primary amines to undergo glycosylation under the action of an acidic promoter, followed by tert-butyl cleavage to obtain the product (Synthesis 2013, 45, 27–39). This method 1) requires the amino group to be converted to tert-aminomethyl tert-butyl ester before the reaction can proceed, and 2) the reaction system contains a strong electrophilic reagent (trifluoromethanesulfonic anhydride), which is incompatible with the amino group. This method cannot achieve one-step direct glycosylation modification of amines.

[0004] Kyung Woon Jung et al. reported a method for synthesizing carbamates at room temperature via a three-component coupling reaction of amines, carbon dioxide, and haloalkanes in a polar aprotic solvent, in the presence of a base and with the promotion of tetrabutylammonium iodide (TBAI) (J. Org. Chem. 2001, 66, 1035-1037; Tetrahedron, 2002, 58, 3329-3347). The authors demonstrated through detailed control experiments that the key to the success of the reaction lies in the additive TBAI, which may play a role in converting inert chloroalkanes and bromoalkanes into reactive iodoalkanes via halogen exchange reactions before participating in the reaction. Daniel Riemer et al. reported a method for synthesizing carbamates at room temperature using a three-component coupling reaction of amines, carbon dioxide, and halogenated hydrocarbons (ChemSusChem 2016, 9, 1916-1920). However, the applicability of halogenated hydrocarbons in this type of method is limited to highly reactive halogenated hydrocarbons such as primary alkyl iodides, benzyl bromide, and carbonyl α-bromines. Coupling reactions of less reactive secondary alkyl halides and chlorinated compounds at room temperature have not been reported. This reaction imposes strict restrictions on the structure of haloalkanes and presents several challenges: 1) As a special class of electrophiles, the reactivity of haloglycosides is closely related to various factors, including the type of substituent on the sugar ring, the type of halogen atom, the type of nucleophile reacting with it, and the degree of reactivity matching between the nucleophile and electrophile. This makes it difficult to accurately predict the reaction results of haloglycosides with various types of nucleophiles, compared to alkyl halides (see Org. Lett. 2015, 17, 11, 2836–2839); 2) As a class of chiral compounds, sugars exhibit anomeric stereoselectivity in substitution reactions between their corresponding haloglycosides and oxygen nucleophiles. Certain types of haloglycosides can undergo specific S-reactions with specific types of oxygen nucleophiles under alkaline conditions. N Type 2 substitution reactions yield products with inverted configurations. However, for other types of halogenated glycosides reacting with oxygen nucleophiles under alkaline conditions, the products are highly dependent on the reaction conditions, yielding a mixture of two angiomeric epimers of the sugar ring (Russian Chemical Bulletin, International Edition, Vol. 65, No. 11, pp. 2776-2778). Furthermore, the nucleophilic reactivity of carbamates relative to halogenated glycosides is unknown, making it difficult to predict their anomeric stereoselectivity in reaction with halogenated glycosides. 3) Nucleophilic substitution reactions between halogenated glycosides and oxygen nucleophiles under alkaline conditions, even if strictly following the S... NType II substitution reactions yield products with inverted configurations. However, due to the potential for haloglycosides to undergo halide-catalyzed isomerization under certain reaction conditions (J. Am. Chem. Soc. 1975, 97, 14, 4056–4062), a mixture of two haloglycosides with different activities is obtained, making it difficult to accurately predict the stereoselectivity of the reaction. In summary, achieving the stereoselective synthesis of 1-O-glycosylcarbamates via a triplet coupling reaction using amines, carbon dioxide, and haloglycosides presents significant challenges and uncertainties. There is an urgent need in this field to develop simpler, more efficient methods for preparing 1-O-glycosylcarbamates with a wider substrate range and higher stereoselectivity. Summary of the Invention

[0005] The technical problem to be solved by this invention is to overcome the shortcomings of existing methods for preparing 1-O-glycosyl carbamates, which require pre-conversion of the glycosyl or amino moieties, are cumbersome in operation, have unstable glycosylation or amination reagents, are difficult to separate and purify, have low reaction efficiency, and are difficult to control the stereoconfiguration of the 1-position of the glycosyl group in the product. Therefore, this invention provides a method for preparing 1-O-glycosyl carbamates. The preparation method of this invention can efficiently synthesize 1-O-glycosyl carbamates and has one or more advantages selected from the following: readily available reactants, simple operation, good reaction effect, and stereospecific yield of 1-O-glycosyl carbamates.

[0006] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0007] This invention provides a method for preparing 1-O-glycosylcarbamate compounds, comprising the following steps:

[0008] (1) In a solvent, under alkaline conditions, amine compounds are subjected to carbamate reaction with carbon dioxide;

[0009] (2) After the reaction in step (1) is completed, the glycosylation reaction is carried out with the halogenated glycoside to obtain the corresponding 1-O-glycosyl carbamate compound;

[0010] The amine compounds are compounds containing primary amine (-NH2) or secondary amine (-NH-) groups, and the N atom in the primary or secondary amine group is connected to at least one sp3 hybridized C atom, and it is not directly connected to carbonyl (-C(=O)-), O, N, S, P heteroatoms or heteroaryl groups.

[0011] The halogenated glycoside is a glycoside containing a carbon-halogen bond at the 1-position of the sugar ring, including substituted α-D-glucopyranoside, substituted 2-fluoro-2-deoxy-α-D-glucopyranoside, substituted 6-fluoro-6-deoxy-α-D-glucopyranoside, substituted α-D-galactopyranoside, substituted α-D-glucopyranoside, substituted β-D / L-arabinopyranoside, and substituted α- -D / L-pyranoxyloside, substituted α-D / L-pyranofucose haloside, or substituted α-D / L-pyranoside cellobiose haloside; when the halogen in the haloside is chlorine, the substituents are each independently selected from acetyl, benzoyl, benzyl, methoxy-substituted benzyl, allyl, or fully substituted 1-glycosyl; when the halogen in the haloside is bromine or iodine, the substituents are each independently selected from acetyl, benzoyl, or fully substituted 1-glycosyl.

[0012] In some embodiments, the halogenated glycoside is a substituted α-D-glucopyranoside, a substituted 2-fluoro-2-deoxy-α-D-glucopyranoside, a substituted 6-fluoro-6-deoxy-α-D-glucopyranoside, a substituted α-D-galactopyranoside, a substituted β-D / L-arabinopyranoside, a substituted α-D / L-xylopyranoside, a substituted α-D / L-fucoside, or a substituted α-D / L-cellobiose glycoside. When the halogen in the halogenated glycoside is chlorine, each substituent is independently selected from acetyl, benzyl, or a fully substituted 1-glycosyl group. When the halogen in the halogenated glycoside is bromine or iodine, the substituent is acetyl.

[0013] In some embodiments, when the halogen glycoside has a substituent at the 2-position, the relative configuration of the substituent and the halogen substituent at the 1-position is 1,2-cis.

[0014] In some embodiments, when the halogenated glycoside is in the α configuration, the glycosidic bond of the corresponding 1-O-glycosylcarbamate compound is in the β configuration.

[0015] In some embodiments, when the halogenated glycoside is in the β configuration, the glycosidic bond of the corresponding 1-O-glycosylcarbamate compound is in the α configuration.

[0016] In some embodiments, each of the fully substituted 1-glycosyl groups is independently selected from fully substituted β-D-glucosyl, fully substituted α-D-glucosyl, fully substituted β-D-galactosyl, fully substituted α-D-galactosyl, fully substituted β-D-mannosyl, fully substituted α-D-mannosyl, fully substituted β-D-xylose, fully substituted α-D-xylose, fully substituted β-D-2-glucosyl, and fully substituted α-D- 2-Aminoglucosyl, fully substituted α-L-rhamnosyl, fully substituted β-L-rhamnosyl, fully substituted α-D-ribosyl, fully substituted β-D-ribosyl, fully substituted α-L-ribosyl, fully substituted β-L-ribosyl, fully substituted α-D-arabinose, fully substituted β-D-arabinose, fully substituted α-L-arabinose, fully substituted β-L-arabinose, fully substituted α-L-fucosyl, fully Substituted β-L-fucosyl, fully substituted β-D-glucuronic acid, fully substituted α-D-glucuronic acid, fully substituted β-D-galacturonic acid, fully substituted α-D-galacturonic acid, fully substituted β-2-deoxy-D-glucosyl, fully substituted α-2-deoxy-D-glucosyl, fully substituted β-2-deoxy-D-galactosyl, fully substituted α-2-deoxy-D-galactosyl, fully substituted α-2-deoxy-D-galactosyl O-D-ribosyl, fully substituted β-2-deoxy-D-ribosyl, fully substituted α-2-deoxy-L-ribosyl, fully substituted β-2-deoxy-L-ribosyl, fully substituted β-2-(acetylamino)-2-deoxy-D-glucosyl, fully substituted α-2-(acetylamino)-2-deoxy-D-glucosyl; wherein the fully substituted groups on the glycosyl group are each independently selected from acetyl, benzoyl, benzyl or p-methoxybenzyl.

[0017] In some embodiments, the solvent is one or more of sulfur-containing compound solvents, nitrogen-containing compound solvents, hydrocarbon solvents, haloalkane solvents, ketone solvents, or ester solvents; preferably, the sulfur-containing compound solvent is dimethyl sulfoxide, the nitrogen-containing compound solvent is one or more of N,N-dimethylformamide, N-methylpyrrolidone, and acetonitrile, the hydrocarbon solvent is one or more of benzene, toluene, and xylene, the haloalkane solvent is one or more of dichloromethane, trichloromethane, 1,2-dichloroethane, trifluorotoluene, chlorobenzene, and fluorobenzene, the ketone solvent is acetone, and the ester solvent is ethyl acetate; more preferably, the solvent is dimethyl sulfoxide and / or N,N-dimethylformamide.

[0018] In some embodiments, the base is one or more of inorganic and organic bases; preferably, the inorganic base is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, and potassium phosphate, and the organic base is one or more of triethylamine, N,N-diisopropylethylamine, dimethylaminopyridine, and 1,8-diazabicycloundec-7-ene; more preferably, the base is cesium carbonate and / or potassium carbonate.

[0019] In some embodiments, the number of primary amine (-NH2) or secondary amine (-NH-) groups in the amine compound may be one or more, for example, 1, 2, 3, 4 or 5.

[0020] In some embodiments, the molar volume ratio of the amine compound to the solvent is 0.01 mol / L to 10.0 mol / L, preferably 0.01 mol / L to 4 mol / L.

[0021] In some embodiments, the molar ratio of the amine compound to the base, based on the number of primary or secondary amine groups it contains, is 1:1 to 1:5; preferably 1:1.5.

[0022] In some implementations, CO2 may be added via a bubbling process.

[0023] In some embodiments, the partial pressure of CO2 is 0.01-2 MPa; preferably 0.1 MPa.

[0024] In some embodiments, the temperature of the carbamate reaction is 10-40°C, preferably room temperature.

[0025] In some embodiments, the carbamate reaction takes 5 min to 48 h, preferably 2 h to 6 h.

[0026] In some embodiments, the reaction process can be carried out by thin-layer chromatography (TLC), 1 Monitoring was performed using 1H NMR or high-performance liquid chromatography (HPLC).

[0027] In some embodiments, the carbamate reaction can be performed without any post-processing steps and can be directly used for the next reaction.

[0028] In some embodiments, the glycosylation reaction takes 5 min to 48 h, preferably 1 h to 24 h.

[0029] In some embodiments, the molar ratio of the amine compound to the halogen glycoside, based on the number of primary or secondary amine groups it contains, is 1:1 to 1:5; preferably 1:1 to 1:3.

[0030] In some embodiments, the glycosylation reaction is carried out at a temperature of 10-40°C, preferably at room temperature.

[0031] In some embodiments, the molar volume ratio of the haloglycoside to the solvent is 0.01 mol / L to 10 mol / L, preferably 0.01 mol / L to 4 mol / L.

[0032] In some embodiments, after the glycosylation reaction is completed, post-processing steps are also included: quenching, washing, organic solvent extraction, and concentration. For example, the reaction solution is quenched with water, washed with saturated ammonium chloride, extracted with dichloromethane, dried with anhydrous sodium sulfate, filtered, and concentrated.

[0033] In some embodiments, the method for preparing the 1-O-glycosylcarbamate compound includes the following steps:

[0034] (1) In a solvent, under alkaline conditions, the amine compound is subjected to a carbamate reaction with carbon dioxide to obtain a reaction system containing carbamate compounds.

[0035] (2) After the reaction in step (1) is completed, the solution of halogenated glycoside and solvent is added to the reaction system in step (1) to carry out glycosylation reaction and obtain the corresponding 1-O-glycosyl carbamate compound.

[0036] In some embodiments, the reagents for the glycosylation reaction are the carbamic acid compound, the halogenated glycoside, and the solution; or, the reagents for the glycosylation reaction are the carbamic acid compound, the halogenated glycoside, the base, and the solution.

[0037] In some embodiments, the group attached to the primary amine (-NH2) or secondary amine (-NH-) in the amine compound may be a group formed by linking one or more substituents selected from the following: alkyl, alkenyl, alkynyl, cyano, heteroalkyl, cycloalkyl, heterocycloalkyl, heterocycloalkenyl, aryl, and heteroaryl; when the group is formed by linking multiple substituents, the substituents may be the same or different (when the group is formed by linking multiple substituents, the number and position of the substituents are not limited, as long as such linking produces a stable compound; when the substituents are linked in a two-ring system, they may be fused, bridged, or spirobicyclic systems); the substituents are optionally connected by one or more R 1 replace;

[0038] R 1 It can be a substituent conventional in the art, as long as it does not affect the reaction, such as halogens, halogenated Cs, etc. 1-10Alkyl, -OH, -CN, -SH, -NO2, -C(=O)-NH2, -S(=O)-NH2 or =O (i.e., the two hydrogen atoms on the carbon atom are replaced by the O group);

[0039] “Miscellaneous” represents N (e.g., ), O (e.g., -O- or =O), S (e.g., -S- or =S), -C(=O)-, -C(=S)-, -S(=O)-, -S(=O)2-, -C(=O)O-, The number of heteroatoms or heterogroups is selected from 1, 2, 3, 4, 5 or 6.

[0040] In some embodiments, the alkyl group in the group is independently C10. 1-20 Alkyl group, preferably C 1-10 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0041] In some embodiments, the alkenyl group is independently C 2-6 Alkenyl group, preferably C 2-4 alkenyl, for example

[0042] In some embodiments, the alkynyl group is independently C 2-6 Alkyne group, preferably C 2-4 Alkyne group, such as ethynyl group.

[0043] In some embodiments, the cyano group is independently C 2-6 Cyano group, preferably C 2-4 Cyano, for example

[0044] In some embodiments, the heteroalkyl group is independently C 1-19 Heteroalkyl, preferably C 2-9 Heteroalkyl groups, wherein one, two, three, or four heteroatoms or heterogroups are selected from N, O, S, S(=O), or S(=O)2; for example (For example) ),

[0045] In some embodiments, the cycloalkyl group is independently C 3-20 Cycloalkyl, preferably C 3-10 cycloalkyl; for example (For example) ),

[0046] In some embodiments, the heterocyclic alkyl group is independently C10. 3-20 Heterocyclic alkyl groups, preferably C5-9 Heterocyclic alkyl groups containing 1, 2, 3, or 4 heteroatoms or heterogroups selected from N, O, S, S(=O), or S(=O)2; for example, piperidinyl (e.g. or ),

[0047] In some embodiments, the heterocyclic alkenyl group is independently C 3-19 Heterocyclic alkenyl groups, preferably C 5-9 Heterocyclic alkenyl groups, containing 1, 2, 3, or 4 heteroatoms or heterogroups selected from N, O, S, S(=O), or S(=O)2; for example

[0048] In some embodiments, the aryl group is independently C 6-20 Aryl, preferably C 6-14 Aryl groups, such as phenyl, benzyl, naphthyl, or biphenyl.

[0049] In some embodiments, the heteroaryl group is independently C 5-19 heteroaryl, preferably C 5-9 Heteroaryl groups, containing 1, 2, 3, or 4 heteroatoms or heterogroups selected from N, O, S, S(=O), or S(=O)2; for example, pyrrole (e.g., ... ), thiophene group (e.g.) ), furanyl (e.g.) ), pyridyl (e.g.) ), indole (e.g.) ) or imidazole group (e.g. ).

[0050] In some embodiments, the method for preparing the 1-O-glycosylcarbamate compound includes the following steps:

[0051] (1) In a solvent, under alkaline conditions, through the presence of I A or I B The amine compounds or their salts of the structural fragments shown undergo carbamate reaction with carbon dioxide;

[0052] (2) After the reaction in step (1) is completed, react with the reaction containing formula III. A or III B The halogenated glycosides of the structural fragments shown undergo glycosylation to yield the corresponding 1-O-glycosylcarbamate compounds.

[0053]

[0054] Wherein, Formula III A or III BIn the compounds with the shown structural fragments, X is independently selected from one of chlorine, bromine, and iodine;

[0055] When X is chlorine, R 1 R 5 Each is independently selected from hydrogen, fluorine, or -OR A Among them, R A Each is independently selected from acetyl, benzoyl, benzyl, methoxy-substituted benzyl, allyl, or fully substituted 1-glycosyl, preferably, R 1 R 5 Each is independently selected from fluorine or -OR A R A Each is independently selected from acetyl, benzyl, or fully substituted 1-glycosyl groups, more preferably, R 1 R 5 Each is independently selected from fluorine or -OR A R A Each is independently selected from acetyl or benzyl;

[0056] R 2 R 3 R 6 R 7 Each is independently selected from methyl or -OR B Among them, R B Each is independently selected from acetyl, benzoyl, benzyl, methoxy-substituted benzyl, allyl, or fully substituted 1-glycosyl, preferably, R B Each is independently selected from acetyl, benzyl, or fully substituted 1-glycosyl groups, more preferably, R B Each is independently selected from acetyl or benzyl;

[0057] R 4 R 8 Each is independently selected from methyl, -CH2-F, -COOCH3, or -OR. C Among them, R C Each is independently selected from acetyl, benzoyl, benzyl, methoxy-substituted benzyl, allyl, or fully substituted 1-glycosyl, preferably, R C Each is independently selected from acetyl, benzyl, or fully substituted 1-glycosyl groups, more preferably, R C Each is independently selected from acetyl or benzyl;

[0058] When the halogen in the halogen glycoside is bromine or iodine, R 1 R 5 Each is independently selected from hydrogen, fluorine, or -OR A Among them, R A Each is independently selected from acetyl, benzoyl, or fully substituted 1-glycosyl groups, preferably R 1 R5 Each is independently selected from fluorine or -OR A R A Each is independently selected from acetyl or fully substituted 1-glycosyl groups, more preferably, R 1 R 5 Each is independently selected from fluorine or -OR A R A Each is independently selected from acetyl groups;

[0059] R 2 R 3 R 6 R 7 Each is independently selected from methyl or -OR B Among them, R B Each is independently selected from acetyl, benzoyl, allyl, or fully substituted 1-glycosyl groups, preferably R B Each is independently selected from acetyl or fully substituted 1-glycosyl groups, more preferably, R B Each is independently selected from acetyl groups;

[0060] R 4 R 8 Each is independently selected from methyl, -CH2-F, -COOCH3, or -OR. C Among them, R C Each is independently selected from acetyl, benzoyl, allyl, or fully substituted 1-glycosyl groups, preferably R C Each is independently selected from acetyl or fully substituted 1-glycosyl groups, more preferably, R C Each is independently selected from acetyl groups.

[0061] In some embodiments, the I A The compounds represented by the structural fragments shown are each independently selected from...

[0062] R aa Each was independently selected from C 1-20 Alkyl, C 6-20 Aryl and halogenated C 5-19 heteroaryl, C 7-25 Alkyl-C 6-20 Aryl, C 1-6 Alkyl-C 5-19 heteroaryl, C 3-20 cycloalkyl, C 5-20 Heterocyclic alkyl groups, wherein the heteroaryl or heterocyclic alkyl group has 1-5 heteroatoms, wherein the heteroatoms are independently N, O or S atoms, preferably R aa Each was independently selected from C 1-6 Alkyl-C 5-9 heteroaryl, halogenated C5-9 heteroaryl, more preferably, R aa Each independently selected

[0063] R ac Each was independently selected from C 3-20 cycloalkyl, C 6-20 Aryl, -CO-C 6-12 heteroaryl-halogenated C 1-3 Alkyl, -C 1-6 alkylene-O-methyl substituted C 6-20 The aryl group, wherein the heterocyclic alkyl group has 1-5 N, O or S atoms, preferably C 3-12 cycloalkyl, C 6-12 Aryl, -CO-C 6-10 heteroaryl-CF3,-C 1-3 alkylene-O-methyl substituted C 6-12 Aryl, more preferably, R ac Each independently selected

[0064]

[0065] R ad Each was independently selected from C 1-20 Alkyl, C 6-12 Aryl, C 6-10 cycloalkyl, halogenated C 6-12 Aryl, preferably, R ad C 1-6 Alkyl, halogenated phenyl, more preferably, R ad Methyl,

[0066] R ae Each is independently selected from -C 1-20 Alkyl-COO-C 1-6 Alkyl-C 6-12 Aryl, -C 1-20 Alkyl-C 6-12 Aryl, -C 1-20 Alkyl-C 6-12 heteroaryl, -C 1-20 Alkyl-NH-COO-C 1-6 Alkyl-C 6-12 Aryl, -C 1-20 Alkyl-C 6-12 Aryl-OC 1-6 Alkyl-C 6-12 Aryl, -C 1-20 Alkyl-C 6-12 heteroaryl-halogenated C 1-6 Alkyl, -C 1-20 alkyl-guanidinyl-nitro, -C1-6 Alkylene (C 1-6 alkyl)-C 1-20 Alkyl, -C 1-6 Alkyl-halogenated C 6-12 Aryl group, wherein the heteroaryl group has 1-5 N, O or S atoms, preferably R ae Each is independently selected from -C 1-6 Alkyl-COO-C 1-6 Alkyl-C 6-10 Aryl, -C 1-6 Alkyl-C 6-10 Aryl, -C 1-6 Alkyl-C 6-10 heteroaryl, -C 1-6 Alkyl-NH-COO-C 1-6 Alkyl-C 6-10 Aryl, -C 1-6 Alkyl-C 6-10 Aryl-OC 1-6 Alkyl-C 6-10 Aryl, -C 1-6 Alkyl-C 6-10 heteroaryl-halogenated C 1-3 Alkyl, -C 1-6 alkyl-guanidinyl-nitro, -C 1-6 Alkylene (C 1-6 alkyl)-C 1-6 Alkyl, -C 1-6 Alkyl-halogenated C 6-12 Aryl, more preferably, R ae Each independently selected

[0067] R ab R af Each independently selected from -OC 1-20 Alkyl-C 6-12 Aryl, -OC 6-12 Aryl, -OC 1-20 Alkyl, -NH-(COO-C 1-20 Alkyl)C 1-10 Alkyl-C 6-12 Aryl, preferably, R ab R af Each independently selected from -OC 1-6 Alkyl-C 6-10 Aryl, -OC 6-10 Aryl, -OC 1-6 Alkyl, -NH-(COO-C 1-6 Alkyl)C 1-6 Alkyl-C 6-10 Aryl, more preferably, Raf Each independently selected

[0068] R ag Each was independently selected from C 6-20 cycloalkyl, C 6-20 Heterocyclic alkyl groups, wherein the heterocyclic alkyl groups have 1-5 N, O or S atoms, preferably R ag Each was independently selected from C 6-12 cycloalkyl, C 6-10 Heterocyclic alkyl groups, wherein the heterocyclic alkyl group has 1-3 N, O or S atoms; more preferably, R ag Each independently selected

[0069] R ah Each is independently selected from hydrogen, -COO-C 1-20 Alkyl group, -COO-CH(C) 1-20 Alkyl)3,-halogenated C 1-6 Alkyl,-methyl substituted C 6-12 heteroaryl-C 1-6 Alkyl-C 6-12 Aryl-C 2-4 Cyano, preferably, R ah Each is independently selected from hydrogen, -COO-C 1-6 Alkyl, -COO-C 1-6 Alkylene (C 1-3 Alkyl)3,-halogenated C 1-3 Alkyl,-methyl substituted C 6-12 heteroaryl-C 1-3 Alkyl-C 6-12 Aryl-C 2-4 Cyano, more preferably, R ah Each is independently selected from H,

[0070] The I B The compounds represented by the structural fragments shown are each independently selected from...

[0071] R ba Each is independently selected from H and C. 1-20 Alkyl, C 2-6 alkenyl, C 1-6 Alkyl-halogenated C 5-12 heteroaryl, -C 1-6 alkyl-sulfonic acid group-C 1-6 Alkyl, preferably, R ba Each is independently selected from H and C. 1-6 Alkyl, C 2-4alkenyl, -C 1-3 Alkyl-halogenated C 5-9 heteroaryl, -C 1-3 alkyl-sulfonic acid group-C 1-3 Alkyl, more preferably, R ba Each is independently selected from H,

[0072] R bb Each independently selected from halogenated C 6-20 Aryl, -C 6-20 Aryl-OC 1-6 Alkyl, C 6-20 Aryl, -C 6-20 Aryl-O-halogenated C 1-6 Alkyl, -C 1-6 Alkyl-C 5-19 heteroaryl, -C 6-20 Aryl-halogenated C 5-19 heteroaryl, -C 2-6 alkenyl-C 5-19 heteroaryl, -C 1-6 Alkyl-CH(C) 5-19 (heteroaryl)-OC 6-20 Aryl, -C 6-20 Aryl-C 5-19 heteroaryl-amino substituted C 5-19 heteroaryl-C 6-20 aryl-sulfonic acid-C 1-6 Alkyl, -C 5-19 heteroaryl (halogenated C) 6-20 aryl)-sulfonic acid-C 5-19 heteroaryl, -C 1-6 Alkyl-CH(C) 6-20 aryl)-O-methyl substituted C 6-20 Aryl, -C 5-19 heteroaryl-C 5-19 heteroaryl-NH-halogenated C 6-20 Aryl-OC 1-6 Alkyl-halogenated C 6-20 Aryl, preferably, R bb Each independently selected from halogenated C 6-12 Aryl, -C 6-12 Aryl-OC 1-3 Alkyl, C 6-12 Aryl, -C 6-12 Aryl-O-halogenated C 1-3 Alkyl, -C 1-3 Alkyl-C 10-16 heteroaryl, -C 6-12 Aryl-halogenated C 10-16 heteroaryl, -C 2-4alkenyl-C 10-16 heteroaryl, -C 1-3 Alkyl-CH(C) 5-12 (heteroaryl)-OC 6-12 Aryl, -C 6-12 Aryl-C 5-12 heteroaryl-amino substituted C 5-19 heteroaryl-C 6-12 aryl-sulfonic acid-C 1-3 Alkyl, -C 5-12 heteroaryl (halogenated C) 6-12 aryl)-sulfonic acid-C 5-12 heteroaryl, -C 1-3 Alkyl-CH(C) 6-12 aryl)-O-methyl substituted C 6-12 Aryl, C 5-12 heteroaryl-C 5-12 heteroaryl-NH-halogenated C 6-12 Aryl-OC 1-3 Alkyl-halogenated C 6-12 Aryl, more preferably, R bb Each independently selected

[0073] When R ba With R bb When combined with the NH atoms attached to them to form a 9- to 14-membered heteroaromatic ring, wherein the 9- to 14-membered heteroaromatic ring has 1, 2, 3 or 4 heteroatoms selected from N, O or S as ring atoms, and the 9- to 14-membered heteroaromatic ring is unsubstituted or has 1, 2, 3 or 4 heteroatoms independently selected from -OC 1-20 Alkyl, halogen, and halogenated C 1-6 Alkyl, nitro, C 2-6 Cyano, C 1-6 Alkyl, -C 6-20 Aryl-OC 1-6 Alkyl substitution, preferably, the 9- to 12-membered heteroaromatic ring has 1, 2, 3, or 4 N atoms as ring atoms, and the 9- to 12-membered heteroaromatic ring is unsubstituted or independently selected from -OC. 1-6 Alkyl, chlorinated, and halogenated C 1-3 Alkyl, cyano, nitro, C 2-4 Cyano, C 1-3 Alkyl, -OC 1-3 Alkyl, -C 6-12 Aryl-OC 1-3 Alkyl substitution, more preferably, R ba With R bb They combine with the NH4+ they are attached to to form

[0074] When R ba With R bb When combined with the NH atoms attached to them to form 5- to 10-membered heterocyclic alkanes, wherein the 5- to 10-membered heterocyclic alkanes have 1, 2, 3 or 4 heteroatoms selected from N, O or S as ring atoms, and the 5- to 10-membered heterocyclic alkanes are formed by 1, 2, 3 or 4 independently selected from C 5-19 heteroaryl, -CH(C 6-20 aryl)-halogenated C 6-20 Aryl, C 5-19 heteroaryl, -COO-C 1-6 Alkyl, -CO-C 6-20 Aryl, -C 6-20 Aryl-amide substituted C 6-20 Aryl, -C 6-20 aryl-S-methyl substituted C 6-20 Aryl, C 1-6 Alkyl groups and -O-CH(C) 1-6 alkyl)-methyl substituted C 6-20 Aryl-NH-halogenated C 5-19 heteroaryl-NH-C 6-20 Aryl-sulfonic acid group -CH(C) 1-6 alkyl)-C 1-6 Alkyl, halogenated C 6-20 Aryl, -C 1-6 Alkyl-OC 5-19 heteroaryl, =(halogenated C) 9-19 (heteroaryl), -sulfonic acid-C 5-19 heteroaryl, -C 1-6 alkyl-methoxy substituted C 6-20 Aryl, -C 5-19 heteroaryl-amino substituted C 5-19 Heteroaryl-O-CH(C) 1-6 (alkyl)-halogenated C 6-20 Aryl, -amido-C 5-19 heteroaryl-SC 1-6 Alkyl-C 5-19 heteroaryl-C 1-6 Alkyl, α-amido-CH(C) 2-6 (alkynyl)-C 1-6 Alkyl-C 6-20 aryl-methyl substituted C 5-19 Heteroaryl substitution, preferably, the 6- to 8-membered heterocyclic alkane has 1, 2, 3, or 4 heteroatoms selected from N or O as ring atoms, and the 6- to 8-membered heterocyclic alkane is independently selected from C. 5-10 heteroaryl, -CH(C 6-12 aryl)-halogenated C 6-12Aryl, -C 10-16 heteroaryl, -COO-C 1-3 Alkyl, -CO-C 6-12 Aryl, -C 6-12 Aryl-amide substituted C 6-12 Aryl, -C 6-12 aryl-S-methyl substituted C 6-12 Aryl, -C 1-3 Alkyl groups and -O-CH(C) 1-3 alkyl)-methyl substituted C 6-12 Aryl-NH-halogenated C 5-10 heteroaryl-NH-C 6-12 Aryl-sulfonic acid group -CH(C) 1-3 alkyl)-C 1-3 Alkyl, halogenated C 6-12 Aryl, -C 1-3 Alkyl-OC 5-10 heteroaryl, -C 2-4 alkenyl-halogenated C 10-16 heteroaryl, -sulfonic acid group -C 5-10 heteroaryl, -C 1-3 alkyl-methoxy substituted C 6-12 Aryl, -C 5-10 heteroaryl-amino substituted C 5-10 Heteroaryl-O-CH(C) 1-3 (alkyl)-halogenated C 6-12 Aryl, -amido-C 5-10 heteroaryl-SC 1-3 Alkyl-C 5-10 heteroaryl-C 1-3 Alkyl, α-amido-CH(C) 1-3 Alkyl-C 2-4 (alkynyl)-C 1-3 Alkyl-C 6-12 aryl-methyl substituted C 5-10 Heteroaryl substitution, more preferably, R ba With R bb They combine with the NH4+ they are attached to to form

[0075] When R ba With R bb When combined with the NH groups to which they are attached to form 5- to 14-membered bridged heterocyclic alkanes, the 5- to 14-membered bridged heterocyclic alkanes are optionally separated by one or more independent components selected from -COO-C. 1-6 Alkyl substituents, preferably, the 5- to 14-membered bridged heterocyclic alkane is optionally replaced by -COO-C 1-3 Alkyl substituent substitution, more preferably, R ba With Rbb They combine with the NH4+ they are attached to to form

[0076]

[0077] When R ba With R bb When R combines with the NH4+ they are attached to to form a 9- to 20-membered heteroaryl ring, preferably, R2... ba With R bb Together with the NH4+ they are attached to, they form 9 to 16-membered heteroaryl rings, more preferably, R4+. ba With R bb They combine with the NH4+ they are attached to to form

[0078]

[0079] When R ba With R bb When combined with the NH4+ molecules attached to them to form 5- to 20-membered heterocyclic alkanes, the 5- to 20-membered heterocyclic alkanes are optionally separated by one or more independently selected from -COO-C(C4)2-C4 ... 1-6 The alkyl group is substituted with a substituent of (3), preferably, the 5 to 20-membered heterocyclic alkane is replaced with -COO-C(C 1-3 Alkyl)3 substituent, more preferably, R ba With R bb They combine with the NH4+ they are attached to to form

[0080] When R ba With R bb When R combines with the NH4+ they are attached to to form a 9- to 20-membered heteroaryl ring, preferably, R2... ba With R bb Together with the NH4+ they are attached to, they form 9 to 16-membered heteroaryl rings, more preferably, R4+. ba With R bb They combine with the NH4+ they are attached to to form

[0081]

[0082] R bc R be R bf Each was independently selected from C 6-20 Aryl-OC 1-6 Alkyl, R bd Each independently selected from -OC 1-6 Alkyl, preferably, R bc Each was independently selected from C 6-12 Aryl-OC 1-3 Alkyl, R bdEach independently selected from -OC 1-3 Alkyl, more preferably, R bc for R bd for

[0083] R bh Each is independently selected from H and C. 1-6 Alkyl, R bi Each was independently selected from C 1-6 Alkyl, C 6-20 Aryl, R bg Each was independently selected from C 1-6 Alkyl-C 6-20 Aryl-halogenated C 1-6 Alkyl, -C 1-6 Alkyl-N (methoxy-substituted C) 6-20 (aryl)-C 5-19 heteroaryl-C 5-19 heteroaryl-C 1-6 Alkyl, α-amido-CH(C) 4-12 cycloalkyl)-CO-C 4-12 Heterocyclic alkyl-C 5-19 Heteroaryl-CO-halogenated C 6-20 Aryl, -C 1-6 alkyl-amino substituted C 5-19 Heteroaryl-S-halogenated C 5-19 Heteroaryl, preferably, R bh Each is independently selected from H and C. 1-3 Alkyl, R bi Each was independently selected from C 1-3 Alkyl, C 6-12 Aryl, R bg Each was independently selected from C 1-3 Alkyl-C 6-12 Aryl-halogenated C 1-3 Alkyl, C 1-3 Alkyl-N (methoxy-substituted C) 6-12 (aryl)-C 5-19 heteroaryl-C 5-10 heteroaryl-C 1-3 Alkyl, amide -CH(C) 4-12 cycloalkyl)-CO-C 4-12 Heterocyclic alkyl-C 5-10 Heteroaryl-CO-halogenated C 6-12 Aryl, C 1-3 alkyl-amino substituted C 5-10 Heteroaryl-S-halogenated C 5-10 heteroaryl, more preferably, R bh Each is independently selected from H, methyl, and R. biEach is independently selected from methyl, naphthyl, R bg each independently

[0084] When R bi R bg When R combines with the NH groups they are attached to to form 5- to 10-membered heterocyclic alkanes, bh Each is independently selected from -C 1-6 alkyl-amide-(-OC) 1-6 Alkyl-halogenated C 1-6 alkyl) substituted C 6-20 Aryl, C 5-10 The heteroaryl group, preferably, when R bi R bg When R combines with the NH4+ molecules they are attached to to form a 6-membered heterocyclic alkane, bh Each is independently selected from -C 1-3 alkyl-amide-(-OC) 1-3 Alkyl-halogenated C 1-3 alkyl) substituted C 6-12 Aryl, C 5-10 More preferably, when R bi R bg When R combines with the NH4+ molecules they are attached to to form a 6-membered heterocyclic alkane, bh Each independently selected

[0085] When R bh R bi Together with the atoms they are attached to, they form C 6-20 Aryl or halogenated C 6-20 aryl-substituted C 6-20 When aryl, R bg Each was independently selected from C 2-4 Alkyne group, H, preferably, when R bh R bi Together with the atoms they are attached to, they form C 6-12 Aryl or halogenated C 6-12 aryl-substituted C 6-12 When aryl, R bg Each was independently selected from C 2-4 Alkyne group, H, more preferably, R bh R bi Together with the atoms they are connected to form At that time, R bg Each is independently selected from H,

[0086] R bj Selected from -C6-20 Aryl-OC 1-6 Alkyl-halogenated C 6-20 Aryl, R bk Selected from C 1-6 Alkyl, R bl Selected from amino groups, preferably R bj Selected from -C 6-12 Aryl-OC 1-3 Alkyl-halogenated C 6-12 Aryl, R bk Selected from C 1-3 Alkyl, R bl Selected from amino, more preferably, R bj for R bk Selected from methyl, R bl Selected from amino groups;

[0087] When R bn R bo When R forms a 5- to 10-membered heterocyclic alkane with N, bm Each is independently selected from C-substituted aminomethyl groups. 6-20 Aryl, -O-CH(C 1-6 Alkyl)3, preferably, when R bn R bo When R forms a 5- to 6-membered heterocyclic alkane with N, bm Each is independently selected from amino-methyl substituted C 6-12 Aryl, -O-CH(C 1-3 Alkyl)3, more preferably, when R bn R bo When R forms a 5- to 6-membered heterocyclic alkane with N, bm Each independently selected

[0088] R bp R bq R br R bs Together with the NH groups they are attached to, they form 5- to 10-membered bridged heterocyclic alkanes, preferably, R bp R bq R br R bs Together with the NH groups they are attached to, they form 8-membered bridged heterocyclic alkanes, more preferably, R bp R bq R br R bs They combine with the NH4+ they are attached to to form

[0089] When R bu R bvWhen R combines with the NH4+ they are attached to to form 4- to 8-membered heterocyclic alkanes, bt Each was independently selected from C 1-6 Alkyl, R bw Each is independently selected from -C 5-19 Heteroaryl-amide group, preferably, when R bu R bv When R combines with the NH4+ molecules they are attached to to form a 5-membered heterocyclic alkane, bt Each was independently selected from C 1-3 Alkyl, R bw Each was independently selected from C 5-10 Heteroaryl-amide group, more preferably, when R bu R bv When R combines with the NH4+ molecules they are attached to to form a 5-membered heterocyclic alkane, bt For methyl, R bw for

[0090] R bx Each was independently selected from C 1-6 Alkylene, -CH(C) 1-6 Alkyl)2,R by Each is independently selected from H, -amide group C 5-19 heteroaryl-NH-C 1-6 Alkyl-C 5-19 Heteroaryl, preferably, R bx Each was independently selected from C 1-3 Alkylene, -CH(C) 1-3 Alkyl)2,R by Each is independently selected from H, amide group -C 5-10 heteroaryl-NH-C 1-6 Alkyl-C 5-10 heteroaryl, more preferably, R bx Each is independently selected as -CH2, -CH(CH)2, R by Each is independently selected from H,

[0091] In some embodiments, the statement as shown in Formula I A The primary amine compound of the structural fragment shown is any of the following compounds:

[0092]

[0093] In some implementations, such as Formula I B The secondary amine compound of the structural fragment shown is any of the following compounds:

[0094]

[0095]

[0096]

[0097] In some implementations, the III A or III B The haloglycoside of the structural fragment shown is any of the following compounds:

[0098]

[0099] Preferably, the formula III A The compound represented by the structural fragment is any one of the following compounds:

[0100]

[0101]

[0102] As in Formula III B The compound represented by the structural fragment is any one of the following compounds:

[0103]

[0104] In some embodiments, the formula IV is as follows A The compound represented by the structural fragment is any one of the following compounds:

[0105]

[0106]

[0107] In some implementations, such as Formula IV B The compound represented by the structural fragment is any one of the following compounds:

[0108]

[0109]

[0110]

[0111]

[0112] On the other hand, the present invention also provides a compound as shown in Formulas 3-85.

[0113]

[0114] On the other hand, the present invention also provides a pharmaceutical composition comprising the compound shown in Formulas 3-85 and a pharmaceutically acceptable carrier.

[0115]

[0116] On the other hand, the present invention also provides the use of compounds as shown in Formulas 3-85 in the preparation of antitumor drugs;

[0117]

[0118] In some embodiments, the tumor is ROS1-positive advanced non-small cell lung cancer (NSCLC).

[0119] As used herein, the choice of pharmaceutically acceptable carriers varies depending on the route of administration and characteristics of action, and may typically be fillers, diluents, binders, wetting agents, disintegrants, lubricants, emulsifiers, or suspending agents.

[0120] In this specification, groups and their substituents may be selected by those skilled in the art to provide stable structural moieties and compounds. When a substituent is described by a conventional chemical formula written from left to right, the substituent also includes chemically equivalent substituents obtained when the structural formula is written from right to left.

[0121] As used herein, the term “substituted” means that any one or more hydrogen atoms on a particular atom are replaced by a substituent, including deuterium and hydrogen variants, provided that the valence state of the particular atom is normal and the substituted compound is stable.

[0122] As used herein, the term "substituted" means that one or more hydrogen atoms in the given structure are substituted by a specific substituent. Further, when the group is substituted by more than one of the said substituents, the substituents are independent of each other; that is, the more than one substituent can be different or the same. Unless otherwise indicated, a substituent can be substituted at each substituted position of the substituted group. When more than one position in the given structural formula can be substituted by one or more substituents selected from a specific group, the substituents can be substituted at the same or different positions.

[0123] As used herein, the term “total substitution” means that all hydrogen atoms in a given structure are replaced by specific substituents.

[0124] As used herein, the term "halogenated glycoside" refers to a glycoside containing a carbon-halogen bond at the 1-position of the sugar ring. Chlorinated glycosides, bromoglycosides, and iodoglycosides are preferred.

[0125] As used herein, the term "pyranose" refers to a sugar having a pyran ring structure, i.e., the condensation of the 5-hydroxyl group of the sugar with the 1-aldehyde group to form a six-membered ring hemiacetal.

[0126] As used herein, the term "alkyl" refers to a straight-chain or branched saturated aliphatic hydrocarbon group. The term "C"... 1-20 "Alkyl" refers to a straight-chain or branched alkyl group having 1 to 20 carbon atoms, preferably C12. 1-6 Alkyl groups (i.e., straight-chain or branched alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms), more preferably C46. 1-3 alkyl.

[0127] As used herein, the term "alkylene" refers to a saturated divalent hydrocarbon group obtained by removing two hydrogen atoms from a saturated straight-chain or branched hydrocarbon group. Examples of alkylene groups include methylene (-CH2-), ethylene {including -CH2CH2- or -CH(CH3)-}, isopropylene {including -CH(CH3)CH2- or -C(CH3)2-}, and so on.

[0128] As used herein, the term "alkoxy" refers to a group having an -O-alkyl structure, wherein the alkyl group is defined as described above.

[0129] As used herein, the term "alkenyl" refers to an alkyl group as defined above that has one or more carbon-carbon double bonds at any point in the chain, and the term "C" refers to an alkyl group having one or more carbon-carbon double bonds at any point in the chain. 2-6 "Alkenyl" refers to an alkenyl group having 2 to 6 carbon atoms and at least one (e.g., 1 to 2) carbon-carbon double bond.

[0130] As used herein, the term "alkynyl" refers to an alkyl group as defined above that has one or more carbon-carbon triple bonds at any point in the chain, and the term "C" refers to an alkyl group. 2-6 "Alkyne" refers to an alkynyl group having 2 to 6 carbon atoms and at least one (e.g., 1 to 2) carbon-carbon triple bond.

[0131] As used in this article, the term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0132] As used in this article, the term "halogenated" refers to fluorinated, chlorinated, brominated, or iodinated products.

[0133] As used herein, the terms "cycloalkyl" and "cycloalkyl ring" are used interchangeably to refer to saturated monocyclic or polycyclic cyclic hydrocarbon groups, including monocyclic cycloalkyl, spirocyclic, fused cycloalkyl, and bridged cycloalkyl groups. The terms "3- to 20-membered cycloalkyl" or "C" are also used. 3-20 "Cycloalkyl" refers to cycloalkyl groups having 3 to 20 ring carbon atoms, including monocyclic cycloalkyl, fused cycloalkyl, and bridged cycloalkyl.

[0134] As used herein, the terms "bridged cycloalkyl" and "bridged cycloalkyl ring" refer to polycyclic cyclic hydrocarbon groups formed by two or more monocyclic rings sharing two non-directly connected carbon atoms. Based on the number of rings formed, they can be classified as bicyclic, tricyclic, tetracyclic, or polycyclic bridged cycloalkyl. The terms "5- to 20-membered bridged cycloalkyl" and "C" are also used. 5-20 "Bridged cycloalkyl" refers to a polycyclic hydrocarbon group with 5 to 20 ring carbon atoms, in which any two rings share two carbon atoms that are not directly connected.

[0135] As used herein, the terms “heterocyclic alkyl” and “heterocyclic alkyl ring” are used interchangeably to refer to cyclic hydrocarbon groups that are saturated or partially unsaturated monocyclic or polycyclic, including, for example, monocyclic heterocyclic alkyl, spirocyclic alkyl, fused heterocyclic alkyl and bridged heterocyclic alkyl.

[0136] As used herein, the terms “fused heterocyclic alkyl” and “fused heterocyclic alkyl ring” refer to a polycyclic heterocyclic alkyl group formed by two or more saturated or partially unsaturated monocycles sharing an adjacent pair of ring atoms, wherein one or more (e.g., 1, 2, or 3) ring atoms are heteroatoms selected from nitrogen, oxygen, or S(=O)m' (where m' is an integer from 0 to 2), and the remaining ring atoms are carbon. When the heteroatom is a nitrogen atom, the nitrogen atom may be substituted or unsubstituted (i.e., N or NR, where R is hydrogen or another substituent as defined herein). Each monocycle may contain one or more double bonds, but no ring has a fully conjugated π-electron system. The shared adjacent pair of ring atoms may be C-C or NC. Depending on the number of constituent rings, they can be classified as bicyclic, tricyclic, tetracyclic, or polycyclic fused heterocyclic alkyl groups.

[0137] As used herein, the terms “bridged heterocyclic alkyl” and “bridged heterocyclic alkyl ring” refer to a polycyclic heterocyclic alkyl group formed by two or more saturated or partially unsaturated monocyclic rings sharing two non-directly connected ring atoms, wherein one or more (e.g., 1, 2, or 3) ring atoms are heteroatoms selected from nitrogen, oxygen, or S(=O)m' (where m' is an integer from 0 to 2), and the remaining ring atoms are carbon. Bridged alkyl groups can be classified as bicyclic, tricyclic, tetracyclic, or polycyclic based on the number of rings formed. The term “5- to 20-membered bridged heterocyclic alkyl” refers to a saturated or partially unsaturated polycyclic heterocyclic alkyl group having 5 to 20 ring atoms, wherein any two rings share two non-directly connected ring atoms, each monocyclic ring may contain one or more double bonds, but none of the rings has a fully conjugated π-electron system.

[0138] As used herein, the terms "aryl," "aryl ring," and "aromatic ring" are used interchangeably to refer to an all-carbon monocyclic, all-carbon non-fused polycyclic (rings connected by covalent bonds, not fused), or all-carbon fused polycyclic (i.e., rings sharing adjacent carbon atom pairs) group, wherein at least one ring in the group is aromatic, i.e., has a conjugated π-electron system. The term "C" 6-14"Aryl" refers to an aryl group having 6 to 14 ring atoms. In this invention, C 6-14 Aryl groups include monocyclic aryl groups, non-fused polycyclic aryl groups, and aromatic fused polycyclic groups. Examples of monocyclic aryl groups include phenyl groups, and examples of non-fused polycyclic aryl groups include biphenyl groups.

[0139] As used herein, the terms "heteroaryl," "heteroaryl ring," and "heteroary ring" are used interchangeably to refer to a monocyclic or fused polycyclic (i.e., sharing adjacent ring atom pairs, which may be CC or NC) group in which the ring atom is substituted by at least one heteroatom independently selected from nitrogen, oxygen, or sulfur, wherein the nitrogen and sulfur atoms may optionally be oxidized, and the nitrogen atom may optionally be quaternized. The heteroaryl group has 6, 10, or 14 shared π electrons, and at least one ring in the group is aromatic. The term "C" is used in conjunction with the term "C" in this context. 5-19 "Heteroaryl" refers to a heteroaryl group having 5 to 19 ring atoms, of which 1, 2, 3 or 4 ring atoms are selected from nitrogen, oxygen or S(=O)m' (where m' is an integer from 0 to 2).

[0140] Those skilled in the art will understand that, according to the conventions used in the art, the structural formulas of the descriptive groups described in this application... This refers to the fact that the corresponding group is connected to other fragments or groups in the compound through this site.

[0141] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0142] The reagents and raw materials used in this invention are all commercially available.

[0143] The positive and progressive effects of this invention are as follows: the preparation method of this invention can efficiently synthesize 1-O-glycosylcarbamate compounds, the reaction raw materials are readily available, the operation is simple, the reaction effect is good, and 1-O-glycosylcarbamate compounds can be obtained stereospecifically. Detailed Implementation

[0144] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0145] Example 1

[0146] Preparation of compound 3-1:

[0147]

[0148] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-1 was prepared according to the following method.

[0149] 2-1 (200 mg, 1.03 mmol), cesium carbonate (509 mg, 1.553 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (468.4 mg, 1.14 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1) to give a white solid product 3-1 (370 mg, 63%), which was in a single β configuration. (c0.1,CHCl3); 1 H NMR (500MHz, CDCl3): δ6.63-6.56(m,2H),5.71-5.64(m,1H),5.31-5.25(m,1H),5.24-5.18(m,1H),5.14(t,J=9.6Hz,1H),4.62-4.40(m,2H), 4.34-4.28(m,1H),4.14-4.07(m,1H),3.90-3.80(m,7H),3.74-3.55(m ,2H),2.82-2.62(m,2H),2.08(s,3H),2.03(s,3H),2.02-2.00(m,6H); 13 C NMR (126MHz, CDCl3): δ170.77,170.19,169.60,169.56,169.54,153.04,152.88,147.93, 147.89,126.08,126.02,124.62,124.40,111.50,109.16,109.13,93.37,72.82,72.77,7 2.60,72.57,70.26,70.24,68.06,68.01,61.60,61.56,56.13,56.11,56.08,56.07,45.71,45.52,42.05,41.98,28.45,28.01,20.87,20.78,20.73,20.72,20.69.HRMS(ESI) calculated value C 26 H 33 NO 13 Na[M+Na] + 590.1848, measured value 590.1844.

[0150] Example 2

[0151] Preparation of compound 3-2:

[0152]

[0153] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-2 was prepared according to the following method.

[0154] 2-2 (215 mg, 1.30 mmol), cesium carbonate (635 mg, 1.95 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Bromoglycoside 1-2 (801.9 mg, 1.95 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-3:1-1:1) to give a white solid product 3-2 (266 mg, 38%), which was in a single β configuration. (c0.1,CH2Cl2); 1 H NMR (600MHz, CDCl3) δ8.19(ddd,J=4.9,2.0,0.9Hz,1H),7.50(ddd,J=8.9,7.2,2.0Hz,1H),6.75–6.58(m,2H),5.65(d,J=8.3Hz,1H),5.28(t,J =9.5Hz,1H),5.19(dd,J=9.7,8.3Hz,1H),5.14(dd,J=10.1,9.3Hz,1H),4.32(dd,J=12.5,4.3Hz,1H),4.12(dd,J=12.6,2.2Hz,1H),3.86(ddd,J

[0155] =10.1,4.3,2.2Hz,1H),3.72–3.50(m,7H),3.42(dd,J=12.5,6.7Hz,1H),2.08(s,3H),2.04–2.03(m,6H),2.02(s,3H); 13C NMR (151MHz, CDCl3) δ 170.77, 170.19, 169.59, 169.48, 159.06, 152.80, 148.07, 137.90, 114.11, 107.46, 93.51, 72.70, 72.64, 70.26, 68.05, 61.58, 45.13, 44.99, 43.89, 43.65, 20.88, 20.76, 20.73, 20.72. HRMS (ESI) calculated C 24 H 31 N3O 11 Na[M+Na] + 560.1858, measured value 560.1851.

[0156] Example 3

[0157] Preparation of compound 3-3:

[0158]

[0159] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-3 was prepared according to the following method.

[0160] 2-3 (200 mg, 1.01 mmol), cesium carbonate (493.6 mg, 1.51 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (830.6 mg, 2.02 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-1:1) to give a white solid product 3-3 (428 mg, 74%), which was in a single β configuration. (c0.1,CH2Cl2); 1H NMR (600MHz, CDCl3): δ5.70–5.59(m,1H),5.27(td,J=9.4,4.3Hz,1H),5.19(dd, J=9.7,8.4Hz,1H),5.16–5.10(m,1H),4.33–4.23(m,1H),4.19–3.96(m,4H),3.8 4(dddd,J=14.3,10.0,4.3,2.2Hz,1H),3.51–3.26(m,2H),2.61–2.55(m,1H),2. 09–2.07(m,3H),2.06–2.04(m,2H),2.03–2.00(m,9H),1.42(s,3H),1.41(s,6H); 13 C NMR (151MHz, CDCl3): δ 170.76, 170.22, 170.20, 169.58, 169.48, 156.12, 154.27, 93.26, 93.21, 80.80, 80.51, 72.81, 72.78, 72.66, 72.47, 70.38, 70.03, 68.08, 68.01, 61.64, 61.58, 58.10, 57.58, 45.84, 28.58, 28.40, 28.36, 20.88, 20.83, 20.81, 20.73, 20.71, 20.64. HRMS (ESI) calculated C 25 H 36 N2O 13 Na[M+Na] + 595.2112, measured value 595.2110.

[0161] Example 4

[0162] Preparation of compounds 3-4:

[0163]

[0164] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-4 were prepared according to the following method.

[0165] 2-4 (200 mg, 0.7 mmol), cesium carbonate (342.1 mg, 1.05 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (575.7 mg, 1.4 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-3:1-1:1) to give a white solid product 3-4 (362.2 mg, 78%), which was in a single β configuration. (c0.1,CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.36–7.31(m,4H),7.30–7.23(m,4H),7.22–7.18(m,1H),5.59(d,J=8.3Hz ,1H),5.26(t,J=9.5Hz,1H),5.12(ddd,J=12.6,9.9,8.8Hz,2H),4.31(dd,J=12.5,4.2Hz,1H),4 .21(s,1H),4.10(dd,J=12.5,2.2Hz,1H),3.84(ddd,J=10.1,4.2,2.2Hz,1H),3.59–3.32(m,4H) ,2.47–2.30(m,3H),2.23(ddd,J=11.2,6.9,3.1Hz,1H),2.08(s,3H),2.02(s,3H),2.00(s,6H); 13 C NMR (151MHz, CDCl3) δ 170.77, 170.18, 169.58, 169.38, 152.68, 141.58, 140.78, 133.00, 129.23, 128.95, 128.89, 127.88, 127.58, 93.41, 75.27, 72.67, 72.60, 70.20, 68.04, 61.58, 51.47, 51.33, 44.32, 44.15, 20.88, 20.72, 20.70. HRMS (ESI) calculated C 32 H 37 ClN2O 11 Na[M+Na] + 683.1985, measured value 683.1978.

[0166] Example 5

[0167] Preparation of compounds 3-5:

[0168]

[0169] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-5 were prepared according to the following method.

[0170] 2-5 (200 mg, 0.86 mmol), cesium carbonate (420 mg, 1.29 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (707.3 mg, 1.72 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:1-1:1). The resulting mixture was subjected to column chromatography again (DCM:MeOH = 100:1) to give a white solid product 3-5 (294 mg, 56%), which was in a single β configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ7.34(bs,0.53H),7.13–7.01(m,3H),5.69(d,J=8.4Hz,0.41H),5.66(d,J=8.2Hz,0.58H),5.33–5.24(m,1 H),5.22–5.13(m,1.62H),5.08(t,J=9.8Hz,0.44H),4.92(d,J=4.3Hz,0.56H),4.80(d,J=5.8Hz,0.41H),4.33(dd,J=12.5,4.3Hz ,0.55H),4.29–3.97(m,2.47H),3.91–3.78(m,1H),3.21–3.02(m,1H),2.49–2.28(m,1H),2.23(s,2.85H),2.20(s,3.50H),2.10( s,1.68H),2.08(s,1.42H),2.05–2.00(m,6.51H),1.95(s,1.31H),1.93(s,1.86H),1.82–1.66(m,3.65H),1.59–1.45(m,1.54H); 13C NMR (151MHz, CDCl3): δ170.75,170.60,170.15,169.75,169.71,169.57,169.55,169.09,168.53 ,154.76,153.00,135.46,135.19,133.61,133.57,128.40,128.36,127.61,127.49,94.01,93.76 ,72.76,72.62,72.60,72.46,70.52,70.31,67.97,67.95,61.58,61.39,55.33,54.73,42.66,42.61,26.22,26.01,24.79,20.89,20.79,20.71,20.69,20.62,20.29,20.16,18.68.HRMS(ESI) calculated value C 29 H 38 N2O 12 Na[M+Na] + 629.2325, measured value 629.2317.

[0171] Example 6

[0172] Preparation of compounds 3-6:

[0173]

[0174] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-6 were prepared according to the following method.

[0175] 2-6 (100 mg, 0.339 mmol), cesium carbonate (265.7 mg, 0.51 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (278.8 mg, 0.678 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-3:1-1:1). Methanol was added, and the mixture was allowed to stand overnight. Filtering yielded a white solid product 3-6 (152 mg, 67%), which was in a single β configuration. (c 0.1, CH2Cl2); 1H NMR (600MHz, CDCl3): δ7.54–7.49(m,1H),7.41–7.37(m,1H),7.37–7.33(m,1H),7.33–7.29(m,2H),7.21–7.15(m,1H),7.09–7.05(m 1H),6.93–6.88(m,1H),5.69–5.58(m,1H),5.28(t,J=9.5Hz,0.63H),5.20–5.04(m2H),4.34–4.28(m ,1H),4.15–4.07(m,1H),3.89–3.80(m,1H),3.76–3.35(m,8H),2.11–2.06(m,4H),2.05–2.00(m,8H); 13 C NMR (151MHz, CDCl3): δ172.07,171.39,171.35,171.30,170.80,170.19,169.76,169.61,169.54,169.50,160.82,160.79,160.76,160. 73,153.37,152.84,152.82,148.61,140.21,140.18,134.00,133.96,132.46,132.40,132.38,131.27,131.25,129.34,128.95,128.66, 128.63, 128.09, 128.07, 128.02, 125.39, 123.46, 123.43, 95.71, 93.53, 75.67, 75.63, 75.01, 74.93, 72.67, 72.63, 71.82, 71.80, 70.23, 70.18, 68.04, 67.76, 62.61, 62.06, 61.77, 61.57, 44.02, 43.71, 21.02, 20.96, 20.93, 20.90, 20.83, 20.79, 20.77, 20.73. HRMS (ESI) calculated value C 32 H 36 N3O 11 S[M+H] + 670.2069, measured value 670.2065.

[0176] Example 7

[0177] Preparation of compounds 3-7:

[0178]

[0179] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-7 were prepared according to the following method.

[0180] 2-7 (200 mg, 0.98 mmol), cesium carbonate (479 mg, 1.47 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (806 mg, 1.96 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1–3:1–2:1–1:1) to give product 3-7 (454 mg, 85%), which was a single β-configuration. [α] 2 D 5 = -25.2 (c0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ7.42–7.36(m,1H),7.21–7.16(m,1H),5.67(d,J=8.2Hz,0.41H) ,5.65(d,J=8.2Hz,0.54H),5.31–5.25(m,1H),5.24–5.17(m,1H),5.17–5.10(m,1H),4. 70–4.49(m,2H),4.36–4.26(m,1H),4.16–4.06(m,1H),3.89–3.83(m,1H),3.83–3.68(m ,2H),3.15–2.84(m,2H),2.09–2.06(m,3.21H),2.04–2.01(m,7.63H),1.94(s,1.29H); 13 C NMR (151MHz, CDCl3): δ170.77,170.73,170.21,170.14,169.62,169.58,169.48, 155.10,155.03,152.86,152.78,149.52,149.47,137.07,137.02,127.08,126.8 5,122.41,122.38,93.64,93.59,72.71,72.66,70.31,70.20,68.01,61.54,44.80,44.64,41.56,41.40,31.87,31.48,20.87,20.76,20.74,20.72.HRMS(ESI) calculated value C 23 H27 ClN2O 11 Na[M+Na] + 565.1179, measured value 565.1196.

[0181] Example 8

[0182] Preparation of compounds 3-8:

[0183]

[0184] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-8 were prepared according to the following method.

[0185] 2-8 (105.6 mg, 0.1 mL, 0.76 mmol), cesium carbonate (371.4 mg, 1.14 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (625 mg, 1.52 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1) to give product 3-8 (288.8 mg, 74%), which was in a single β configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ7.24–7.18(m,1H),7.17–7.11(m,1H),7.04–6.98(m,2H),5. 71–5.67(m,1H),5.31–5.24(m,1H),5.22–5.11(m,2H),4.51(d,J=15.6Hz,0.46H), 4.47–4.38(m,1H),4.37–4.26(m,1.51H),4.17–4.10(m,1H),3.89–3.93(m,1H),2. 89(s,1.42H),2.81(s,1.42H),2.09(s,3H),2.04–1.99(m,7.56H),1.92(s,1.40H); 13CNMR (151MHz, CDCl3): δ170.77, 170.22, 169.60, 169.58, 169.45, 169.38, 162.35 (d, J = 246.0Hz), 162 .25(d,J=246.0Hz),154.35,153.80,132.54,132.52,129.83,129.77,129.22,129.17,115.58(d,J=2 1.5Hz), 115.56 (d, J = 21.5Hz), 93.56, 93.49, 77.37, 77.16, 76.95, 72.95, 72.80, 72.68, 72.58, 70.39, 70.18, 68.07, 68.05, 61.62, 61.57, 52.30, 51.84, 34.63, 33.81, 20.88, 20.73, 20.63. HRMS (ESI) calculated value C 23 H 28 FNO 11 Na[M+Na] + 536.1545, measured value 536.1539.

[0186] Example 9

[0187] Preparation of compounds 3-9:

[0188]

[0189] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-9 were prepared according to the following method.

[0190] 2-9 (200 mg, 0.94 mmol), cesium carbonate (459.4 mg, 1.41 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (773 mg, 1.88 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1-1:1) to give product 3-9 (419 mg, 76%), which was in a single β configuration. (c 0.1, CH2Cl2); 1H NMR (600MHz, CDCl3) δ5.65–5.59(m,1H),5.28–5.22(m,1H),5.19–5.05(m,2H),4.34–4.27(m,1H),4.14–4.08(m,1H),3.86–3. 81(m,1H),3.70–3.44(m,4H),3.38–3.11(m,4H),2.89–2.80(m,2H),2.09–2.06(m,3H),2.04–2.00(m,9H),1.46–1.42(m,9H); 13 C NMR (151MHz, CDCl3) δ 170.79, 170.76, 170.18, 169.59, 169.49, 154.52, 154.49, 152.14, 93.14, 79.83, 72.82, 72.79, 72.57, 70.36, 70.24, 68.03, 61.62, 50.31, 50.24, 50.01, 49.87, 49.72, 49.40, 42.42, 41.54, 40.64, 28.59, 20.89, 20.88, 20.82, 20.80, 20.73, 20.71. HRMS (ESI) calculated C 26 H 38 N2O 13 Na[M+Na] + 609.2260, measured value 609.2266.

[0191] Example 10

[0192] Preparation of compound 3-10:

[0193]

[0194] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-10 were prepared according to the following method.

[0195] 2-10 (200 mg, 0.2 mL, 1.16 mmol), cesium carbonate (567 mg, 1.74 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (954 mg, 2.32 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1) to give a white solid product 3-10 (542 mg, 86%), which was in a single β configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ5.66–5.62(m,1H),5.27–5.21(m,1H),5.20–5.15(m,0.65H), 5.13–5.09(m,0.67H),5.08–5.03(m,0.69H),4.31–4.19(m,1.73H),4.13–4.04(m,1 .38H),3.84–3.78(m,1H),3.62–3.56(m,0.33H),3.52–3.37(m,1.67H),2.21–2.10( m,1H),2.09–2.04(m,4H),2.04–1.98(m,9H),1.98–1.82(m,2H),1.46–1.41(m,9H); 13 C NMR (151MHz, CDCl3): δ171.22,171.15,170.77,170.69,170.20,170.17,169.73,169.59, 169.34,152.24,151.98,93.23,92.97,81.76,81.53,72.94,72.75,72.63,72.32,70.45,

[0196] 70.23, 68.08, 68.03, 61.64, 60.04, 59.79, 47.12, 46.75, 30.89, 29.96, 28.09, 27.92, 24.12, 23.37, 20.86, 20.78, 20.75, 20.72, 20.70. HRMS (ESI) calculated value C 24 H 35 NO 13 Na[M+Na] + 568.1997, measured value 568.2001.

[0197] Example 11

[0198] Preparation of compound 3-11:

[0199]

[0200] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-11 was prepared according to the following method.

[0201] 2-11 (200 mg, 0.87 mmol), cesium carbonate (425.2 mg, 1.31 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (715.5 mg, 1.74 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1-1:1) to give a white solid product 3-11 (479 mg, 97%), which was in a single β configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ5.64(d,J=8.3Hz,1H),5.33–5.24(m,1H),5.21–5.08(m,2H),5.04– 4.79(m,2H),4.33–4.24(m,1H),4.24–3.80(m,6H),2.09–2.05(m,3H),2.04–2.00(m,9H); 13 C NMR (151MHz, CDCl3): δ170.72,170.64,170.19,170.03,169.74,169.60,169.47,16 9.27,152.57,152.13,149.73,149.56,143.71(q,J=40.1Hz),118.24(q,J=270.5Hz ), 94.08, 72.79, 72.76, 72.48, 72.28, 70.33, 70.15, 67.88, 67.79, 61.44, 61.36, 43.51, 43.17, 41.47, 41.36, 40.70, 40.36, 20.82, 20.80, 20.71, 20.67. HRMS(ESI) calculated value C 21 H 25 F3N4O 11Na[M+Na] + 589.1364, measured value 589.1364.

[0202] Example 12

[0203] Preparation of compound 3-12:

[0204]

[0205] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-12 were prepared according to the following method.

[0206] 2-12 (1000 mg, 5.17 mmol), cesium carbonate (2526.7 mg, 7.755 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (4251.8 mg, 10.34 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1) to give product 3-12 (2797 mg, 95%), which was in a single β configuration. (c0.1,CH2Cl2); 1 H NMR (600MHz, CDCl3): δ7.20–7.15(m,1H),7.10–7.05(m,1H),6.87–6.80(m,2H),5.74–5.69(m,1H),5.28–5.22 (m,1H),5.21–5.11(m,2H),4.50–4.44(m,1H),4.36–4.29(m,1.50H),4.30–4.21(m,0.62H),4.16–4.08(m,1H), 3.87–3.82(m,1H),3.80–3.77(m,3H),3.33–3.20(m,1H),3.15–3.08(m,0.42H),3.03–2.96(m,0.48H),2.10–2 .06(m,3H),2.06–1.96(m,9H),1.49(p,J=7.5Hz,1H),1.45–1.30(m,1H),1.29–1.18(m,2H),0.91–0.84(m,3H); 13C NMR (151MHz, CDCl3): δ170.79,170.25,169.59,169.35,159.24,159.12,154.38, 153.75,129.48,129.33,129.29,128.74,114.10,93.34,93.32,73.09,73.07,72 .55,72.52,70.35,70.24,68.10,61.65,61.62,55.41,50.25,49.55,46.84,46.12,30.20,29.55,20.87,20.72,20.60,20.10,19.97,13.90,13.87.HRMS(ESI) calculated value C 27 H 37 NO 12 Na[M+Na] + 590.2206, measured value 590.2208.

[0207] Example 13

[0208] Preparation of compound 3-13:

[0209]

[0210] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-13 were prepared according to the following method.

[0211] 2-13 (75 mg, 0.5 mmol), cesium carbonate (244.4 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (411.2 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (DCM:MeOH = 100:1) to give product 3-13 (170 mg, 70%), which was in a single β configuration. (c 0.1, CH2Cl2); 1HNMR (600MHz, CDCl3): δ5.69–5.62(m,1H),5.31–5.24(m,1H),5.19–5.10(m,2H),4.35–4.29(m,1H),4.24–4.07(m,3H),3.88–3.82(m,1H),3.74( d,J=10.9Hz,0.42H),3.71–3.66(m,1H),3.62–3.54(m,2H),3.42(d,J=11 .0Hz,0.55H),2.10–2.07(m,3H),2.06–1.96(m,12H),1.93–1.77(m,1H); 13 C NMR (151MHz, CDCl3): δ 170.77, 170.19, 169.60, 169.49, 169.39, 151.18, 150.59, 93.28, 93.19, 72.71, 72.64, 72.24, 72.15, 71.83, 70.34, 70.30, 68.13, 68.05, 61.63, 61.58, 56.02, 55.99, 55.41, 27.48, 27.34, 26.72, 26.68, 20.88, 20.76, 20.74, 20.72. HRMS (ESI) calculated C 21 H 29 NO 12 Na[M+Na] + 510.1580, measured value 510.1582.

[0212] Example 14

[0213] Preparation of compound 3-14:

[0214]

[0215] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-14 were prepared according to the following method.

[0216] 2-14 (200 mg, 1.12 mmol), cesium carbonate (537.4 mg, 1.68 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (921 mg, 2.24 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1-1:1) to give product 3-14 (528 mg, 85%), which was in a single β configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ8.09–8.00(m,2H),7.31(d,J=8.3Hz,1H),5.69–5.65(m,1H),5.29(t,J =9.5Hz,1H),5.24–5.19(m,1H),5.17–5.11(m,1H),4.77–4.67(m,1.58H),4.62(d,J=17.0Hz, 0.45H),4.33–4.28(m,1H),4.14–4.09(m,1H),3.89–3.83(m,1H),3.81–3.66(m,2H),3.02–2. 94(m,1.51H),2.90–2.83(m,0.49H),2.08(s,3.18H),2.04–2.02(m,7.43H),1.96(s,1.35H); 13 C NMR (151MHz, CDCl3): δ170.76,170.74,170.21,170.16,169.62,169.57,169.45,152. 88,152.80,146.81,141.92,141.90,134.45,134.28,129.95,129.92,121.94,121.78, 121.76, 93.63, 93.59, 72.70, 72.68, 72.65, 70.31, 70.28, 68.03, 67.99, 61.58, 61.53, 45.80, 45.65, 41.36, 41.20, 29.19, 28.82, 20.88, 20.80, 20.74, 20.73. HRMS (ESI) calculated value C 24 H 28 N2O 13 Na[M+Na] +575.1487, measured value 575.1484.

[0217] Example 15

[0218] Preparation of compound 3-15:

[0219]

[0220] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-15 were prepared according to the following method.

[0221] 2-15 (86 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (226 mg, 0.55 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:2-1:1) to give a brown liquid product 3-15 (205.6 mg, 75%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3): δ7.97(s,1H),7.49–7.41(m,1H),7.35–7.28(m,1H),7.19–7.13(m,1H),7.13–7.07(m,1H),5.73–5.66(m,1H),5.35–5.20 (m,2H),5.19–5.11(m,1H),4.78–4.57(m,2H),4.35–4.28(m,1H),4.19– 4.05(m,1H),3.99–3.71(m,3H),2.95–2.68(m,2H),2.10–1.98(m,12H); 13C NMR (126MHz, CDCl3): δ170.86,170.82,170.28,170.19,169.66,169.58,169.45,153.57,152.96,135.90, 135.88,131.42,131.28,125.49,125.37,121.98,119.89,119.88,117.90,117.82,110.87,110.82,106.9 7,106.88,93.44,93.41,72.79,72.67,72.52,72.51,70.26,70.12,68.00,67.90,61.56,61.47,60.55,41.89,41.80,41.75,41.62,23.69,23.18,21.21,20.88,20.82,20.75,20.73,20.53,14.31.HRMS(ESI) calculated value C 26 H 30 N2O 11 Na[M+Na] + 569.1742, measured value 569.1750.

[0222] Example 16

[0223] Preparation of compound 3-16:

[0224]

[0225] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compounds 3-16 were then prepared by the following steps:

[0226] 2-16 (0.125 mL, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 3.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 7:1) to give a white solid product 3-16 (mixed yield 55%), which was in a single β configuration. (c 1.0, CHCl3); 1HNMR (500MHz, CDCl3) δ7.44–7.00(m,24H),5.72(d,J=8.1Hz,1H),4.94(d,J=11.0Hz,1H),4.91–4.83(m,5H),4. 82–4.49(m,1H),4.03–3.92(m,2H),3.89–3.75(m,4H),3.73–3.53(m,3H),2.82–2.70(m,2H),2.02–1.85(m,2H); 13 C NMR (126MHz, CDCl3) δ 153.04, 138.54, 138.15, 138.13, 138.04, 137.79, 128.64, 128.49, 128.46, 128.42, 128.08, 127.99, 127.88, 127.86, 127.78, 127.76, 127.74, 127.72, 126.07, 124.25, 95.90, 84.96, 81.10, 77.38, 75.70, 75.44, 75.06, 74.88, 73.60, 68.17, 44.92, 27.20, 23.49. HRMS (ESI) calculated C 44 H 45 NO7Na[M+Na] + 722.3088, measured value 722.3094.

[0227] Example 17

[0228] Preparation of compound 3-17:

[0229]

[0230] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-17 were prepared according to the following method.

[0231] 2-17 (266 mg, 2.0 mmol), cesium carbonate (980 mg, 3.0 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (3 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Bromoglycoside 1-2 (904 mg, 2.2 mmol) was dissolved in DMSO (3 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:1) to give a white solid product 3-17 (626.4 mg, 62%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR (600MHz, CDCl3): δ7.22–7.16(m,2H),7.15–7.09(m,2H),5.70–5.67(m,1H), 5.31–5.25(m,1H),5.24–5.19(m,1H),5.17–5.10(m,1H),4.70–4.46(m,2H),4.34 –4.29(m,1H),4.13–4.09(m,1H),3.88–3.85(m,1H),3.77–3.57(m,2H),2.94–2.7 1(m,2H),2.08(s,3H),2.03–2.02(m,3H),2.02–2.01(m,4.45H),1.93(s,1.37H); 13 C NMR (151MHz, CDCl3): δ170.78,170.20,170.19,169.60,169.58,169.52,169.50,153.08,1 52.93,134.35,134.32,132.91,132.69,128.83,128.74,126.89,126.64,126.62,126.47, 126.46, 93.39, 72.82, 72.78, 72.60, 72.57, 70.27, 70.26, 68.08, 68.03, 61.62, 61.57, 45.99, 45.82, 41.98, 41.93, 28.93, 28.54, 20.87, 20.76, 20.74, 20.71, 20.65. HRMS (ESI) calculated value C 24 H 29 NO 11 Na[M+Na] + 530.1633, measured value 530.1637.

[0232] Example 18

[0233] Preparation of compound 3-18:

[0234]

[0235] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-18 was prepared according to the following method.

[0236] 2-18 (0.27 mL, 2.0 mmol), cesium carbonate (980 mg, 3.0 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (3 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (1644 mg, 4.0 mmol) was dissolved in DMSO (3 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a brown solid product 3-18 (621.7 mg, 60%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR (500MHz, CDCl3): δ5.63–5.57(m,1H),5.31–5.20(m,1H),5.18–5.05(m ,2H),4.34–4.24(m,1H),4.15–4.01(m,2H),3.98–3.89(m,1H),3.86–3.79( m,1H),3.67(s,3H),3.02–2.80(m,2H),2.47(dp,J=10.3,6.6,6.1Hz,1H),2 .09–2.05(m,4H),2.04–1.98(m,8H),1.95–1.79(m,2H),1.76–1.55(m,2H); 13 C NMR (126MHz, CDCl3): δ 174.72, 174.65, 170.78, 170.19, 169.59, 169.48, 152.70, 152.57, 93.37, 72.73, 72.63, 72.51, 70.19, 70.14, 67.99, 61.54, 52.00, 43.56, 43.47, 43.34, 40.64, 27.99, 27.82, 27.72, 27.61, 20.85, 20.70, 20.68. HRMS (ESI) calculated C 22 H 31 NO 13 Na[M+Na] + 540.1688, measured value 540.1683.

[0237] Example 19

[0238] Preparation of compound 3-19:

[0239]

[0240] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-19 was prepared according to the following method.

[0241] 2-19 (148 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (822 mg, 2.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-3:1) to give a yellow liquid product 3-19 (272.9 mg, 56%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3): δ5.63–5.58(m,1H),5.26–5.18(m,1H),5.15–5.05(m,2H),4.33–4.24(m,1H),4.24–4.11(m,2H),4.11–4 .03(m,1H),3.85–3.78(m,1H),2.05–2.01(m,3H),2.00–1.94(m,9H),1.94–1.79(m,2H),1.75–1.58(m,4H),1.54–1.35(m,4H); 13 C NMR (126MHz, CDCl3): δ 170.64, 170.08, 169.48, 169.47, 169.37, 169.19, 150.68, 150.24, 92.93, 92.84, 72.75, 72.41, 72.36, 70.29, 70.16, 68.12, 67.98, 61.58, 61.51, 54.47, 54.42, 54.19, 31.39, 31.32, 30.59, 30.50, 28.24, 28.02, 27.49, 27.44, 20.74, 20.61, 20.59, 16.61, 16.56. HRMS (ESI) calculated C 22 H 31 NO 11 Na[M+Na] + 508.1789, measured value 508.1796.

[0242] Example 20

[0243] Preparation of compound 3-20:

[0244]

[0245] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-20 was prepared according to the following method.

[0246] 2-20 (158 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (822 mg, 2.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1.8:1) to give a white solid product 3-20 (281.6 mg, 53%), which was in a single β configuration. (c 1.0, CHCl3); 1 HNMR (500MHz, CDCl3): δ7.42–7.33(m,2H),7.22–7.17(m,1H),5.65–5.59(m,1 H),5.27–5.20(m,1H),5.16–5.10(m,1H),5.09–5.03(m,1H),4.65–4.45(m,2H ),4.27–4.20(m,1H),4.07–4.00(m,1H),3.86–3.79(m,1H),3.68–3.58(m,2H) ,2.92–2.71(m,2H),2.02–1.97(m,3H),1.97–1.92(m,7.74H),1.87(s,1.41H); 13 C NMR (126MHz, CDCl3): δ170.45,169.91,169.88,169.36,169.33,169.30,169.22,152.61,152.57,

[0247] 139.78,139.77,134.18,134.00,130.18,130.14,130.03,130.01,129.66,129.59,118.46,118.42,110.33,93.29,93.26,72.36,72.31,70.04,70.03,67.80,67.77,61.35,61.31,45.22,45.10,41.13,41.00,28.93,28.54,20.62,20.55,20.50,20.49,20.46. HRMS(ESI) calculated value C 25 H 28 N2O 11 Na[M+Na] + 555.1585, measured value 555.1590.

[0248] Example 21

[0249] Preparation of compound 3-21:

[0250]

[0251] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-21 was prepared according to the following method.

[0252] 2-21 (74 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (411 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a white solid product 3-21 (232.1 mg, 89%), which was in a single β configuration. (c 1.0, CHCl3); 1HNMR (500MHz, CDCl3): δ7.28–7.15(m,4H),7.12–7.06(m,1H),5.77–5.54(m,2H),5.25–5.17(m,1H),5.15–4.97(m,4H),4.56–4 .45(m,1H),4.35–4.18(m,2H),4.10–4.01(m,1H),3.97–3.79(m,2H),3.71–3.53(m,1H),2.03–1.99(m,3H),1.98–1.90(m,9H); 13 C NMR (126MHz, CDCl3): δ170.48,169.94,169.33,169.31,169.08,169.06,154.04 ,153.60,136.73,136.70,132.48,132.35,132.33,128.55,128.05,127.60,127 .42,127.31,118.04,116.95,93.26,72.75,72.68,72.33,70.06,69.99,67.84,61.38,61.34,49.92,49.09,48.31,20.62,20.50,20.47,20.32.HRMS(ESI) calculated value C 25 H 31 NO 11 Na[M+Na] + 544.1789, measured value 544.1789.

[0253] Example 22

[0254] Preparation of compound 3-22:

[0255]

[0256] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-22 was prepared according to the following method.

[0257] 2-22 (1.12 g, 5.0 mmol), cesium carbonate (2.45 g, 7.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (4.11 g, 10 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a white solid product 3-22 (3.368 g, >99%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR (500MHz, CDCl3): δ7.14–7.09(m,1.23H),7.08–7.03(m,0.69H),6.81–6.76(m,2H),5.71–5.67(m,1H), 5.28–5.02(m,3H),4.76(d,J=14.9Hz,0.64H),4.45(d,J=15.4Hz,0.36H),4.36(d,J=15.5Hz,0.36H),4.31– 4.24(m,1H),4.15–4.01(m,4.68H),3.91(d,J=17.6Hz,0.36H),3.84–3.79(m,1H),3.76(d,J=17.6Hz,0.36 H),3.73–3.71(m,3H),3.48(d,J=18.2Hz,0.62H),2.04–2.01(m,3H),1.99–1.91(m,9H),1.21–1.15(m,3H); 13 CNMR (126MHz, CDCl3): δ170.54,170.51,169.98,169.92,169.52,169.37,169.35,168.82, 168.79,159.35,159.28,154.08,153.89,129.77,129.48,129.30,127.86,114.06,113.80 ,93.59,93.26,72.68,72.49,72.43,70.14,69.77,67.92,67.82,61.43,61.38,61.17,61.12,55.21,51.11,50.54,47.48,46.77,20.60,20.51,20.49,14.08,14.01.HRMS(ESI) calculated value C 27 H 35 NO14 Na[M+Na] + 620.1950, measured value 620.1955.

[0258] Example 23

[0259] Preparation of compound 3-23:

[0260]

[0261] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compounds 3-23 were prepared by the following steps:

[0262] 2-23 (110 mg, 0.3 mmol), cesium carbonate (146.6 mg, 0.45 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (503.2 mg, 3.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1). The resulting mixture was subjected to column chromatography again (DCM:EA = 10:1) to give product 3-23 (141 mg, 53%), which was in a single β configuration. (c 1.0,CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.38–7.21(m,28H),7.17–7.09(m,2H),5.53(d,J=8.1Hz,1H),5.45(d,J=8.1 Hz,1H),5.19–5.11(m,2H),5.08(s,2H),4.89(d,J=10.9Hz,1H),4.83–4.77(m,2H),4.75(d,J=11. 2Hz,1H),4.71(d,J=11.2Hz,1H),4.61(d,J=12.1Hz,1H),4.51(d,J=10.7Hz,1H),4.48–4.41(m,2H ),3.77–3.67(m,4H),3.57–3.50(m,2H),2.50–2.35(m,2H),2.29–2.20(m,1H),2.07–1.98(m,1H); 13CNMR(151MHz,CDCl3)δ172.53,171.41,154.01,138.56,138.20,138.18,138.08 ,135.84,135.19,128.81,128.70,128.55,128.52,128.47,128.42,128.40,128. 08, 128.02, 127.89, 127.87, 127.82, 127.79, 95.61, 84.92, 80.92, 75.87, 75.43, 75.13, 75.08, 73.61, 68.15, 67.60, 66.71, 53.52, 30.17, 27.63. HRMS (ESI) calculated value C 54 H 55 NO 11 Na[M+Na] + 916.3670, measured value 916.3667.

[0263] Example 24

[0264] Preparation of compound 3-24:

[0265]

[0266] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compounds 3-24 were then prepared by the following steps:

[0267] 2-24 (80 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (836.6 mg, 1.5 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1–4:1) to obtain product 3-24 (228 mg, 63%), which was in a single β configuration. (c 0.1, CH2Cl2); 1HNMR(600MHz, CDCl3)δ7.89(s,1H),7.58(d,J=7.9Hz,1H),7.34–7.23(m,18H),7.21–7.16(m, 2H),7.15–7.08(m,3H),6.93(d,J=2.3Hz,1H),5.58(d,J=8.2Hz,1H),4.88(d,J=10.9Hz,1H),4 .86–4.78(m,2H),4.74(q,J=8.2,7.0Hz,1H),4.69(s,2H),4.62(d,J=12.1Hz,1H),4.52(d,J= 10.8Hz,1H),4.47(d,J=12.1Hz,1H),3.77–3.68(m,4H),3.62–3.44(m,4H),2.98–2.93(m,2H); 13 C NMR (151MHz, CDCl3) δ154.41,138.57,138.48,138.22,138.10,136.48,128. 53,128.50,128.43,128.10,128.05,128.02,127.99,127.89,127.81,127.75 ,127.30,122.39,122.33,119.64,118.79,112.62,111.37,95.25,84.93,81.27,75.87,75.28,75.12,74.92,73.62,68.27,41.24,25.58.HRMS(ESI) calculated value C 45 H 46 N₂O₇Na[M+Na] + 749.3201, measured value 749.3197.

[0268] Example 25

[0269] Preparation of compound 3-25:

[0270]

[0271] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compounds 3-25 were prepared by the following steps:

[0272] 2-25 (95 mg, 0.49 mmol), cesium carbonate (239.5 mg, 0.735 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (821.9 mg, 1.47 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1–4:1) to obtain product 3-25 (348 mg, 98%), which was in a single β configuration. [α] 2 D 5 = -0.9 (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.34–7.24(m,18H),7.15–7.10(m,2H),5.54(d,J=8.1Hz,1H),4.89 (d,J=10.9Hz,1H),4.83–4.78(m,2H),4.76–4.71(m,2H),4.63(d,J=12.1Hz,1H),4.52(d, J=10.0Hz,2H),4.46(d,J=12.1Hz,1H),3.77–3.69(m,4H),3.67(s,3H),3.58–3.44(m,3H) ),2.23(tt,J=12.1,3.6Hz,1H),2.13–1.98(m,4H),1.59–1.47(m,2H),1.17–1.07(m,2H); 13 C NMR (151MHz, CDCl3) δ 175.79, 153.49, 138.54, 138.41, 138.20, 138.07, 128.54, 128.51, 128.47, 128.17, 128.08, 128.04, 127.98, 127.87, 127.82, 127.79, 95.11, 84.96, 81.34, 75.87, 75.29, 75.09, 73.60, 68.19, 51.81, 49.64, 42.35, 32.40, 32.26, 27.79. HRMS (ESI) calculated C 43 H 49 NO9Na[M+Na] + 746.3303, measured value 746.3300.

[0273] Example 26

[0274] Preparation of compound 3-26:

[0275]

[0276] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compound 3-26 was prepared by the following steps:

[0277] 2-26 (100 mg, 0.5 mmol), cesium carbonate (245 mg, 0.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (838.6 mg, 1.5 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1) to obtain product 3-26 (261 mg, 68%), which was in a single β configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.33–7.25(m,18H),7.15–7.11(m,2H),5.54(d,J=8.2Hz,1H),4.8 9(d,J=10.9Hz,1H),4.84–4.79(m,2H),4.78–4.71(m,2H),4.63(d,J=12.1Hz,1H),4.57 –4.51(m,2H),4.47(d,J=12.1Hz,1H),4.09–3.95(m,2H),3.77–3.70(m,4H),3.68–3.61 (m,1H),3.60–3.51(m,2H),2.89–2.79(m,2H),1.91(tt,J=8.7,3.5Hz,2H),1.46(s,9H); 13C NMR (151MHz, CDCl3) δ 154.81, 153.53, 138.52, 138.40, 138.18, 138.05, 128.56, 128.53, 128.49, 128.18, 128.10, 128.06, 128.00, 127.90, 127.87, 127.86, 127.82, 95.14, 84.97, 81.30, 79.88, 75.90, 75.33, 75.14, 75.12, 73.62, 68.21, 48.61, 32.30, 28.56. HRMS (ESI) calculated C 45 H 58 N3O9[M+NH4] + 784.4172, measured value 784.4168.

[0278] Example 27

[0279] Preparation of compound 3-27:

[0280]

[0281] Chloroglycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compound 3-27 was prepared by the following steps:

[0282] 2-27 (78 mg, 0.4 mmol), cesium carbonate (195.5 mg, 0.6 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (670.9 mg, 1.2 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1-4:1) to give product 3-27 (124.3 mg, 43%), which was in a single β configuration. (c 0.1, CH2Cl2); 1HNMR (600MHz, CDCl3) δ7.38–7.23(m,18H),7.16–7.12(m,2H),5.53(d,J=8.1Hz,1H),4.96–4.87(m ,2H),4.86–4.78(m,3H),4.75(d,J=11.1Hz,1H),4.63(d,J=12.1Hz,1H),4.53(d,J=10.9Hz,1H),4. 49(d,J=12.1Hz,1H),3.78–3.69(m,3H),3.67(s,3H),3.61–3.51(m,2H),2.09(d,J=14.0Hz,1H),1 .96(d,J=13.9Hz,1H),1.91–1.79(m,2H),1.67–1.61(m,2H),1.49–1.38(m,2H),1.35–1.22(m,2H); 13 C NMR (151MHz, CDCl3) δ 174.49, 153.16, 138.54, 138.35, 138.18, 138.12, 128.57, 128.55, 128.48, 128.41, 128.09, 128.05, 127.92, 127.88, 127.85, 127.79, 95.11, 84.99, 81.07, 75.94, 75.40, 75.17, 75.06, 73.61, 68.20, 59.40, 52.56, 33.05, 32.08, 25.19, 21.39, 21.31. HRMS (ESI) calculated C 43 H 49 NO9Na[M+Na] + 746.3306, measured value 746.3300.

[0283] Example 28

[0284] Preparation of compound 3-28:

[0285]

[0286] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compound 3-28 was prepared by the following steps:

[0287] 2-28 (94 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (838.6 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1) to give product 3-28 (254.8 mg, 71%), which was in a single β configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.36–7.21(m,18H),7.18–7.10(m,2H),5.50(d,J=8.1Hz ,1H),5.05(s,1H),4.89(d,J=10.9Hz,1H),4.85–4.79(m,2H),4.77(d,J=11.5 Hz,1H),4.69(d,J=11.5Hz,1H),4.63(d,J=12.1Hz,1H),4.52(d,J=10.7Hz,1H ),4.47(d,J=12.1Hz,1H),3.79–3.68(m,4H),3.60–3.47(m,2H),2.25(s,6H); 13 C NMR (151MHz, CDCl3) δ 153.12, 138.49, 138.12, 138.01, 128.57, 128.55, 128.51, 128.14, 128.10, 128.03, 127.94, 127.86, 123.38 (q, J = 274.1Hz), 95.10, 84.92, 81.37, 77.37, 77.16, 76.95, 75.89, 75.41, 75.19, 75.16, 73.63, 68.13, 51.46, 45.49, 45.48, 35.09 (q, J = 40.3, 39.7Hz). HRMS (ESI) calculated values ​​C 41 H 42 F3NO7Na[M+Na]+740.2817, measured value 740.2806.

[0288] Example 29

[0289] Preparation of compound 3-29:

[0290]

[0291] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compound 3-29 was prepared by the following steps:

[0292] 2-29 (183 mg, 1.0 mmol), potassium carbonate (207 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated twice to remove CO2, and DMSO (2 mL) was added. The reaction was allowed to proceed at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 1.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction mixture was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1). The resulting mixture was then subjected to column chromatography again (toluene:EA = 25:1) to give a white solid product 3-29 (mixed yield 39%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR (500MHz, CDCl3) δ7.43–7.20(m,18H),7.19–7.11(m,2H),5.60(d,J=8.2Hz,1H),4.93(d,J=10.8Hz,1H),4.88–4.80(m,2H),4.7 7(s,2H),4.67(d,J=12.2Hz,1H),4.58–4.46(m,3H),3.86–3.70(m,5H),3.64–3.52(m,2H),1.67–1.57(m,2H),1.49–1.24(m,20H); 13 C NMR (126MHz, CDCl3) δ153.87,138.55,138.34,138.17,138.07,128.51,128.4 9,128.43,128.19,128.06,128.03,128.00,127.85,127.82,127.79,127.74,9 5.10, 84.94, 81.31, 75.85, 75.29, 75.10, 75.07, 73.56, 68.13, 48.01, 30.63, 30.54, 23.88, 23.84, 23.71, 23.62, 23.57, 23.55, 23.41, 21.51. HRMS (ESI) calculated value C 47 H 59 NO7Na[M+Na]+722.4184, measured value 722.4185.

[0293] Example 30

[0294] Preparation of compound 3-30:

[0295]

[0296] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compounds 3-30 were prepared by the following steps:

[0297] 2-30 (0.148 mL, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 1.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1) to give a white solid product 3-30 (mixed yield 54%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR (500MHz, CDCl3): δ7.41–7.28(m,18H),7.23–7.17(m,2H),5.67–5.61(m,1H), 4.97(d,J=10.9Hz,1H),4.93–4.83(m,3H),4.82–4.78(m,1H),4.72–4.65(m,2H),4 .59(d,J=10.7Hz,1H),4.53(d,J=12.1Hz,1H),3.86–3.75(m,4H),3.71–3.58(m,3H ),1.85–1.66(m,5H),1.42–1.20(m,4H),1.16(d,J=6.9Hz,3H),1.12–0.93(m,2H); 13C NMR (126MHz, CDCl3): δ153.86,153.84,138.50,138.48,138.32,138.18,138.13,138.03,138.00,128.4 5,128.42,128.38,128.15,128.11,128.00,127.97,127.94,127.91,127.78,127.75,127.72,127.68,9 5.08, 94.99, 84.91, 84.85, 81.28, 81.21, 77.36, 75.80, 75.78, 75.27, 75.20, 75.02, 73.49, 73.48, 68.12, 68.09, 51.60, 43.30, 43.16, 29.11, 28.95, 28.88, 26.40, 26.20, 26.17, 18.13, 18.11. HRMS (ESI) calculated value C 43 H 51 NO7Na[M+Na]+716.3558, measured value 716.3564.

[0298] Example 31

[0299] Preparation of compound 3-31:

[0300]

[0301] Chloroglucinol 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compound 3-31 was prepared by the following steps:

[0302] 2-31 (292 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 1.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1) to give a white solid product 3-31 (468.6 mg, 57%), which was in a single β configuration. (c 1.0, CHCl3); 1HNMR(600MHz, CDCl3)δ7.32–7.13(m,26H),7.12–7.08(m,2H),7.03–6.97(m,2H),5. 53(d,J=8.2Hz,1H),5.20(d,J=8.2Hz,1H),5.11–5.04(m,2H),4.86(d,J=10.9Hz,1H) ,4.80–4.75(m,2H),4.72–4.63(m,3H),4.60(d,J=12.1Hz,1H),4.49(d,J=10.7Hz,1 H),4.45(d,J=12.1Hz,1H),3.78–3.64(m,4H),3.56–3.47(m,2H),3.12–3.05(m,2H); 13 C NMR (151MHz, CDCl3) δ170.99,153.73,138.48,138.13,138.06,138.01,135.33,135.06,129.45,128.73,128.69,128.68,128.62,128.47,128. 45,128.43,128.40,128.31,128.03,127.94,127.82,127.78,127.75,1 27.24,95.47,84.92,80.60,77.27,75.80,75.34,75.04,74.89,73.60,

[0303] 68.15, 67.36, 54.87, 38.03. HRMS (ESI) calculated value C 51 H 51 NO9Na[M+Na]+844.3456, measured value 844.3457.

[0304] Example 32

[0305] Preparation of compound 3-32:

[0306]

[0307] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-32 were prepared according to the following method.

[0308] 2-32 (127 mg, 1.0 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (226 mg, 0.55 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1-2:3) to give a brown liquid product 3-32 (69.3 mg, 38%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR(500MHz, CDCl3)δ8.29(s,1H),7.50(d,J=7.9Hz,1H),7.36(d,J=8.1Hz,1H),7.22–7.15(m,1H),7.10(t,J=7.5Hz,1H ),6.99(d,J=2.4Hz,1H),5.67(d,J=8.4Hz,1H),5.47(d,J=7.9Hz,1H),5.24(t,J=9.5Hz,1H),5.17–5.06(m,2H),4.65(dt ,J=8.0,5.5Hz,1H),4.28(dd,J=12.5,4.2Hz,1H),4.23(dd,J=12.5,2.3Hz,1H),3.83(ddd,J=10.2,4.2,2.3Hz,1H),3.69 (s,3H),3.38(dd,J=14.9,5.4Hz,1H),3.28(dd,J=14.8,5.6Hz,1H),2.09(s,3H),2.04(s,3H),2.02(s,3H),2.00(s,3H); 13 C NMR (126MHz, CDCl3) δ 171.84, 170.94, 170.26, 169.63, 169.59, 153.31, 136.21, 127.42, 123.31, 122.38, 119.82, 118.59, 111.43, 109.27, 92.98, 72.94, 72.59, 70.06, 67.93, 61.48, 54.51, 52.66, 27.61, 20.95, 20.74, 20.72. HRMS (ESI) calculated C 27 H 32 N2O 13 Na[M+Na]+615.1797, measured value 615.1800.

[0309] Example 33

[0310] Preparation of compound 3-33:

[0311]

[0312] Chlorinated glycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compounds 3-33 were prepared by the following steps;

[0313] 2-33 (331 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 3.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a white solid product 3-33 (695.0 mg, 81%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR (500MHz, CDCl3) δ7.39–7.28(m,23H),7.21–7.15(m,2H),5.64–5.56(m,2H),5.20–5.02(m,3H) ,4.95(d,J=10.9Hz,1H),4.89–4.83(m,3H),4.78(d,J=11.3Hz,1H),4.63(d,J=12.0Hz,1H),4.55(d ,J=10.8Hz,1H),4.49(d,J=11.9Hz,1H),4.39(td,J=8.1,4.9Hz,1H),3.75(s,6H),3.63–3.58(m,2 H),3.22–3.11(m,2H),1.93–1.82(m,1H),1.77–1.66(m,1H),1.56–1.46(m,2H),1.44–1.34(m,2H); 13C NMR (126MHz, CDCl3) δ172.53,156.59,154.02,138.41,138.07,138.04,137.87,136. 63,128.52,128.41,128.39,128.36,128.35,128.27,128.14,128.08,128.00,127.89 ,127.86,127.77,127.75,127.70,95.42,84.74,80.86,77.28,75.73,75.17,74.96,74.93,73.40,68.17,66.61,53.75,52.44,40.44,31.90,29.34,22.31.HRMS(ESI) calculated value C 50 H 56 N2O 11 Na[M+Na]+883.3776, measured value 883.3781.

[0314] Example 34

[0315] Preparation of compounds 3-34:

[0316]

[0317] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compounds 3-34 were then prepared by the following steps:

[0318] 2-34 (322 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 3.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a white solid product 3-34 (548.6 mg, 64%), which was in a single β configuration. (c 1.0, CHCl3); 1H NMR (500MHz, CDCl3) δ7.55–7.32(m,23H),7.26(dd,J=7.1,2.2Hz,2H),7.15(d,J=8.1Hz,2H),7.01(d,J =8.1Hz,2H),5.72(d,J=8.1Hz,1H),5.42(d,J=8.1Hz,1H),5.08(s,2H),5.02(d,J=10.9Hz,1H),4.98–4 .91(m,2H),4.88(d,J=11.3Hz,1H),4.85–4.80(d,J=11.3Hz,1H),4.78–4.71(m,2H),4.66(d,J=10.8Hz ,1H),4.59(d,J=12.2Hz,1H),3.92–3.81(m,4H),3.78(s,3H),3.71–3.65(m,2H),3.18(d,J=5.5Hz,2H); 13 C NMR (126MHz, CDCl3) δ171.62,157.99,153.70,138.37,138.03,138.00,137.89,13 6.89,130.33,128.52,128.36,128.33,128.25,128.22,127.92,127.85,127.82,1 27.70, 127.68, 127.65, 127.61, 127.45, 115.01, 95.36, 84.78, 80.57, 77.18, 75.68, 75.23, 74.91, 74.80, 73.46, 69.88, 68.05, 54.89, 52.26, 37.00. HRMS (ESI) calculated value C 52 H 53 NO 10 Na[M+Na]+874.3562, measured value 874.3566.

[0319] Example 35

[0320] Preparation of compound 3-35:

[0321]

[0322] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compounds 3-35 were then prepared by the following steps:

[0323] 2-35 (224 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (839 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:1-1:2) to give a white solid product 3-35 (254.4 mg, 52%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3) δ7.44–7.20(m,27H),7.19–7.15(m,2H),7.15–7.09(m,6H),6.83(d,J= 8.0Hz,1H),6.60(d,J=1.4Hz,1H),5.64(d,J=8.1Hz,1H),4.95(d,J=10.9Hz,1H),4.91(d,J =11.0Hz,1H),4.87–4.82(m,2H),4.74(d,J=11.0Hz,1H),4.68–4.62(m,2H),4.57(d,J=10. 8Hz,1H),4.49(d,J=12.1Hz,1H),3.82–3.71(m,4H),3.66–3.56(m,5H),3.18–3.01(m,2H); 13 C NMR (126MHz, CDCl3) δ171.69,154.26,142.28,138.75,138.59,138.18,138.09, 136.29,129.77,128.53,128.41,128.40,128.35,128.33,128.11,127.96,127. 92,127.74,127.68,127.65,127.62,119.62,95.57,84.76,80.93,77.31,75.73,75.34,75.32,75.01,74.91,73.51,68.23,54.36,52.14,29.83.HRMS(ESI) calculated value C 61 H 59 N3O9Na[M+Na]+1000.4144, measured value 1000.4153.

[0324] Example 36

[0325] Preparation of compound 3-36:

[0326]

[0327] Chloroglycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compounds 3-36 were prepared by the following steps:

[0328] 2-36 (270 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 3.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:3) to give a white solid product 3-36 (450.0 mg, 56%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (600MHz, CDCl3) δ7.40–7.26(m,18H),7.19–7.15(m,2H),5.89(bs,1H),5.58( d,J=8.1Hz,1H),4.95(d,J=11.0Hz,1H),4.90–4.75(m,4H),4.59(d,J=12.0Hz,1H) ,4.56–4.48(m,2H),4.45–4.36(m,1H),3.80–3.64(m,9H),3.63–3.57(m,1H),3.3 5(bs,1H),3.26–3.15(m,1H),2.49(bs,1H),2.00–1.89(m,1H),1.81–1.63(m,3H); 13 C NMR (151MHz, CDCl3) δ 172.11, 159.28, 154.92, 138.29, 137.98, 137.84, 137.49, 128.47, 128.42, 128.22, 128.15, 127.95, 127.91, 127.87, 127.79, 95.64, 84.63, 80.64, 77.30, 75.77, 75.13, 75.03, 75.00, 73.38, 68.36, 52.81, 40.34, 30.04, 24.35. HRMS (ESI) calculated C 42 H50 N5O 11 Na[M+Na]+800.3501, measured value 800.3508.

[0329] Example 37

[0330] Preparation of compound 3-37:

[0331]

[0332] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compound 37 was then prepared by the following steps:

[0333] 2-37 (182 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (839 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (toluene:EA = 20:1-10:1) to give a pale yellow solid product 3-37 (268.1 mg, 60%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3) δ7.37–7.12(m,28H),7.01–6.92(m,2H),6.05(d,J=7.5Hz,1H),5.54(d,J=8.1 Hz,1H),5.41(d,J=7.8Hz,1H),4.91(d,J=10.9Hz,1H),4.86–4.80(m,2H),4.78–4.69(m,3H),4.65 (d,J=12.1Hz,1H),4.54(d,J=10.7Hz,1H),4.50(d,J=12.1Hz,1H),4.38(td,J=7.7,5.6Hz,1H),3. 81–3.70(m,4H),3.67(s,3H),3.61–3.54(m,2H),3.14(dd,J=13.8,5.8Hz,1H),3.09–2.96(m,3H); 13C NMR (126MHz, CDCl3) δ171.25,169.93,153.95,138.50,138.14,138.00,136.11,135.5 3,129.53,129.26,128.88,128.71,128.51,128.47,128.41,128.09,127.99,127.98, 127.87, 127.85, 127.81, 127.79, 127.29, 127.27, 95.60, 84.94, 80.70, 77.30, 75.84, 75.37, 75.10, 75.02, 73.64, 68.15, 56.24, 53.57, 52.42, 38.58, 37.93. HRMS (ESI) calculated value C 54 H 56 N2O 10 Na[M+Na]+915.3827, measured value 915.3828.

[0334] Example 38

[0335] Preparation of compound 3-38:

[0336]

[0337] Chloroglycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compounds 3-38 were prepared by the following steps:

[0338] 2-38 (168 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 3.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 10:1) to give a white solid product 3-38 (495.1 mg, 71%), which was in a single β configuration. (c 1.0, CHCl3); 1H NMR (500MHz, CDCl3) δ7.43–7.24(m,18H),7.20–7.14(m,2H),5.60(d,J=8.1Hz,1H),5.32(d,J=9 .1Hz,1H),4.94(d,J=10.9Hz,1H),4.88–4.81(m,3H),4.77(d,J=11.1Hz,1H),4.66(d,J=12.1Hz, 1H),4.56(d,J=10.8Hz,1H),4.52(d,J=12.1Hz,1H),4.35(dd,J=9.1,4.7Hz,1H),3.84–3.71(m,7 H),3.64–3.56(m,2H),2.21(pd,J=6.9,4.8Hz,1H),1.01(d,J=6.9Hz,3H),0.94(d,J=6.9Hz,3H); 13 C NMR (126MHz, CDCl3) δ 172.21, 154.27, 138.49, 138.14, 138.03, 128.51, 128.47, 128.42, 128.41, 128.38, 128.02, 128.00, 127.96, 127.84, 127.82, 127.79, 127.74, 95.47, 84.92, 80.86, 77.33, 75.85, 75.39, 75.08, 75.04, 73.54, 68.09, 59.15, 52.28, 31.36, 19.01, 17.66. HRMS (ESI) calculated C 41 H 47 NO9Na[M+Na]+720.3143, measured value 720.3150.

[0339] Example 39

[0340] Preparation of compound 3-39:

[0341]

[0342] Chloroglycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compounds 3-39 were prepared by the following steps:

[0343] 2-39 (128 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 3.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:1-1:2) to give a white solid product 3-39 (662.3 mg, 95%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3) δ7.38–7.24(m,18H),7.19–7.14(m,2H),6.59(t,J=6.4Hz,1H),6.31(d,J=6.0Hz,1H),5.59(d ,J=8.1Hz,1H),4.93(d,J=10.9Hz,1H),4.88–4.79(m,3H),4.75(d,J=11.2Hz,1H),4.66(d,J=12.1Hz,1H),4.55(d, J=10.8Hz,1H),4.51(d,J=12.1Hz,1H),4.33(ddd,J=11.5,6.0,1.8Hz,1H),3.81–3.72(m,4H),3.64–3.57(m,2H), 3.30–3.17(m,2H),2.21–2.14(m,1H),2.05–1.98(m,1H),1.86–1.71(m,2H),1.61–1.49(m,1H),1.45–1.32(m,1H); 13 C NMR (126MHz, CDCl3) δ 175.06, 153.42, 138.53, 138.16, 138.07, 128.46, 128.45, 128.39, 128.16, 128.03, 127.96, 127.93, 127.81, 127.75, 127.72, 127.70, 95.42, 84.88, 80.99, 77.36, 75.76, 75.35, 75.05, 74.98, 73.51, 68.19, 53.77, 42.13, 31.74, 28.90, 28.04. HRMS (ESI) calculated C 41 H 46 N₂O₈Na[M+Na]+ 717.3146, measured value 717.3151.

[0344] Example 40

[0345] Preparation of compound 3-41:

[0346]

[0347] Chloroglucinol 1-1 was prepared according to the literature (Carbohydrate Research. 2008, 343, 2989-2991), and then compound 3-41 was prepared by the following steps:

[0348] 2-41 (95 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-1 (366 mg, 1.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:3) to give a white liquid product 3-41 (271.0 mg, 96%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3) δ7.43–7.31(m,1H),5.58(d,J=8.3Hz,1H),5.24(t,J=9.5Hz,1H),5.15–5.02(m,1H),4.27(dd,J=12.6,4. 2Hz,1H),4.06(dd,J=12.5,2.3Hz,1H),3.82(ddd,J=10.2,4.2,2.2Hz,1H),3.78–3.22(m,8H),2.03(s,3H),2.00–1.94(m,9H); 13 C NMR (126MHz, CDCl3) δ 170.64, 170.60, 170.02, 169.45, 169.35, 152.52, 135.00, 130.14, 128.65, 127.04, 93.41, 72.42, 72.34, 70.04, 67.76, 61.33, 46.93, 44.03, 41.70, 20.74, 20.64, 20.58, 20.57. HRMS (ESI) calculated C 26 H 32 N2O 12 Na[M+Na]+587.1847, measured value 587.1851.

[0349] If the above experiment is repeated using bromoglycosides 1-2, product 3-41 is obtained in 86% yield.

[0350] Example 41

[0351] Preparation of compound 3-42:

[0352]

[0353] Chloroglycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compounds 3-42 were then prepared by the following steps:

[0354] 2-41 (95 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (839 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1-1:1) to give product 3-42 (350 mg, 92%), which was a single β-configuration. (c 0.1, CH2Cl2); 1 HNMR (600MHz, CDCl3) δ7.47–7.40(m,3H),7.40–7.35(m,2H),7.35–7.25(m,18H),7.16–7.12(m,2H),5.62(d,J=8.1Hz,1H),4.9 8–4.70(m,5H),4.63(d,J=12.1Hz,1H),4.54(d,J=10.8Hz,1H),4.48(d,J=12.1Hz,1H),3.82–3.71(m,4H),3.69–3.11(m,10H); 13C NMR (151MHz, CDCl3) δ 170.71, 153.36, 138.46, 138.26, 138.13, 137.94, 135.31, 130.20, 128.77, 128.57, 128.55, 128.52, 128.13, 127.99, 127.90, 127.89, 127.85, 127.60, 127.18, 95.84, 84.97, 75.78, 75.37, 75.08, 75.01, 73.65, 68.12, 47.36, 44.04, 41.94. HRMS (ESI) calculated C 46 H 48 N₂O₈Na[M+Na] + 779.3307, measured value 779.3303.

[0355] Example 42

[0356] Preparation of compound 3-43:

[0357]

[0358] Bromoglycosides 1-8 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-43 were prepared according to the following method.

[0359] 2-41 (95 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-8 (226 mg, 0.55 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-2:3) to give a pale yellow liquid product 3-43 (211.4 mg, 75%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3) δ7.47–7.35(m,5H),5.59(d,J=8.3Hz,1H),5.42(d,J=3.4Hz,1H),5.40–5.24(m,1H),5 .09(dd,J=10.5,3.4Hz,1H),4.20–4.03(m,3H),3.90–3.27(m,8H),2.15(s,3H),2.03(s,6H),1.99(s,3H); 13C NMR (126MHz, CDCl3) δ 170.79, 170.46, 170.23, 170.06, 169.68, 152.72, 135.13, 130.26, 128.78, 127.16, 94.00, 71.57, 70.61, 67.89, 66.82, 60.98, 47.31, 44.47, 41.89, 20.87, 20.80, 20.76, 20.67. HRMS (ESI) calculated C 26 H 32 N2O 12 Na[M+Na] + 587.1847, measured value 587.1853.

[0360] Example 43

[0361] Preparation of compound 3-44:

[0362]

[0363] Bromoglycosides 1-10 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-44 were prepared according to the following method.

[0364] 2-41 (95 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-10 (218 mg, 0.55 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1) to give a pale yellow liquid product 3-44 (149.1 mg, 54%), which was a single β-configuration. (c 1.0, CHCl3); 1 HNMR(500MHz, CDCl3)δ7.48–7.36(m,5H),5.68(d,J=7.9Hz,1H),5.34(t,J=9.3Hz,1H), 5.25–5.11(m,2H),4.19(d,J=9.8Hz,1H),3.73(s,3H),3.68–3.25(m,8H),2.03(s,9H); 13C NMR (126MHz, CDCl3) δ 170.82, 169.93, 169.60, 169.39, 166.96, 135.17, 130.29, 128.81, 127.19, 93.26, 72.94, 71.61, 70.06, 69.30, 53.17, 20.74, 20.71, 20.59. HRMS (ESI) calculated C 25 H 30 N2O 12 Na[M+Na] + 573.1691, measured value 573.1698.

[0365] Example 44

[0366] Preparation of compound 3-45:

[0367]

[0368] Bromoglycosides 1-6 were prepared according to the literature (Journal of Fluorine Chemistry, 1998, 91, 2, 159-163), and then compounds 3-42 were prepared by the following steps:

[0369] 2-41 (190 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-6 (740 mg, 2.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a white solid product 3-45 (444.2 mg, 85%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR (500MHz, CDCl3) δ7.45–7.32(m,5H),5.63(d,J=8.3Hz,1H),5.28(t,J=9.5Hz,1H),5.11(t,J=9.7Hz,2H),4.50(ddd,J=45.2,10.7,2.4H z,1H),4.41(ddd,J=46.5,10.6,3.9Hz,1H),3.83(dddd,J=23.3,10.2,3.8,2.3Hz,1H),3.76–3.18(m,8H),2.01(s,3H),2.01–1.98(m,6H);13 C NMR (126MHz, CDCl3) δ 170.67,

[0370] 170.09, 169.37, 169.30, 152.57, 135.10, 130.16, 128.69, 127.08, 93.37, 80.59 (d, J = 176.4 Hz), 77.42, 77.16, 76.91, 73.02 (d, J = 19.5 Hz), 72.41, 70.06, 67.61 (d, J = 6.7 Hz), 47.10, 44.01, 41.76, 20.65, 20.61, 20.59. HRMS (ESI) calculated value C 24 H 29 N2O 10 FNa[M+Na]+547.1698, measured value 547.1698.

[0371] Example 45

[0372] Preparation of compound 3-46:

[0373]

[0374] Chloroglucinol 1-12 was prepared according to the literature (Carbohydrate Research, 2008, 343, 17, 2989-2991), and then compound 3-46 was prepared by the following steps:

[0375] 2-41 (48 mg, 0.25 mmol), cesium carbonate (123 mg, 0.375 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (2 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Chloroglucinol 1-12 (221 mg, 0.75 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1–1:2) to give a yellow liquid product 3-46 (108.6 mg, 88%). The product was a mixture of α and β in a ratio of β:α = 12:1. (c 1.0, CHCl3); 1¹H NMR (500MHz, CDCl₃): (a mixture of αβ configurations) δ 7.46–7.20 (m, 5.42H), 6.12 (d, J = 3.6Hz, 0.08H, H₁-α), 5.56 (d, J = 7.1Hz, 1H, H₁-β), 5.33–5.28 (m, 0.08H), 5.16 (t, J = 8.5Hz, 1H), 4.96 (t, J = 7.7Hz, 1.12H), 4.87 (td, J = 8.5, 5.0Hz, 1H), 4.08–4.00 (m, 1H), 3.84–3.04 (m, 10.14H), 1.99–1.91 (m, 9.64H); 13 C1-NMR (126MHz, CDCl3): (a mixture of αβ configurations) δ 170.43, 169.90, 169.63, 169.49, 169.41, 169.19, 152.52, 134.96, 129.94, 128.49, 126.91, 93.50 (C1-β), 90.79 (C1-α), 70.70, 69.36, 69.22, 69.19, 68.37, 68.22, 62.48, 60.51, 47.05, 43.81, 41.66, 20.54, 20.49, 20.42. HRMS (ESI) calculated C1-NMR values. 23 H 28 N2O 10 Na[M+Na]+515.1636, measured value 515.1636.

[0376] If the above experiment is repeated using bromoglycoside 1-11 (prepared according to the literature Organic Letters, 2007, 9, 20, 3897-3900), product 3-41 is obtained in 41% yield.

[0377] Example 46

[0378] Preparation of compound 3-47:

[0379]

[0380] Chloroglucinol 1-14 was prepared according to the literature (Carbohydrate Research, 2008, 343, 17, 2989-2991), and then compound 3-47 was prepared by the following steps:

[0381] 2-41 (95 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-14 (294 mg, 1.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:2-1:2) to give a white solid product 3-47 (248.2 mg, 97%), which was in a single α configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3) δ7.40–7.28(m,5H),5.52(d,J=7.1Hz,1H),5.26–5.18(m,2H),5.08(dd,J=9.5, 3.5Hz,1H),3.94(dd,J=13.1,3.4Hz,1H),3.83–3.13(m,0H),2.05(s,3H),1.98(s,3H),1.95(s,3H); 13 C NMR (126MHz, cdcl3) δ 170.47, 169.95, 169.64, 169.36, 152.62, 135.01, 129.98, 128.53, 126.95, 93.64, 69.56, 68.00, 67.11, 43.84, 20.74, 20.63, 20.52. HRMS (ESI) calculated values ​​C 23 H 28 N2O 10 Na[M+Na]+515.1636, measured value 515.1641.

[0382] Example 47

[0383] Preparation of compound 3-49:

[0384]

[0385] Bromoglycosides 1-16 were prepared according to the literature (Steroids, 1998, 63, 1, 44-49), and then compounds 3-48 were prepared by the following steps:

[0386] 2-41 (190 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-16 (221 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:2) to give a white solid product 3-49 (69%), which was in a single β configuration. (c 1.0, CHCl3); 1 HNMR(500MHz, CDCl3)δ7.46–7.27(m,5H),5.57–5.50(m,1H),5.24–5.16(m,1H),5.11–5.04(m,1H),5.04–4.94(m,2H) ,4.88–4.80(m,1H),4.50–4.38(m,2H),4.34–4.26(m,1H),4.11–3.93(m,3H),3.82–3.12(m,23H),2.09–1.87(m,21H); 13 C NMR (126MHz, CDCl3) δ 170.60, 170.43, 170.20, 170.16, 169.56, 169.53, 169.27, 168.97, 152.50, 135.09, 130.09, 128.63, 127.02, 100.63, 93.32, 75.90, 73.29, 72.84, 71.93, 71.86, 71.47, 70.32, 67.78, 61.57, 43.82, 20.85, 20.63, 20.50, 20.47. HRMS (ESI) calculated C 38 H 48 N2O 20 Na[M+Na]+875.2693, measured value 875.2702.

[0387] Example 48

[0388] Preparation of compound 3-50:

[0389]

[0390] Bromoglycosides 1-5 were prepared according to the literature (Tetrahedron, 2008, 64, 48, 10906-10911), and then compounds 3-50 were prepared by the following steps:

[0391] 2-41 (54 mg, 0.28 mmol), cesium carbonate (139 mg, 0.43 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (2 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Bromoglycoside 1-5 (210 mg, 0.59 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1) to give a white liquid product 3-50 (135.8 mg, 91%), which was in a single β configuration. (c 1.0, CHCl3); 1 HNMR (500MHz, CDCl3) δ7.45–7.34(m,5H),5.75(dd,J=8.2,2.9Hz,1H),5.36(dt,J=14.3,9.3Hz,1H),5.05(t,J=9.7Hz,1H),4.59–4.32(m,1H), 4.28(dd,J=12.6,4.3Hz,1H),4.12–4.04(m,1H),3.85(ddd,J=10.2,4.3 ,2.2Hz,1H),3.81–3.28(m,8H),2.05(s,3H),2.04(s,3H),2.00(s,3H); 13 C NMR (126MHz, CDCl3) δ 170.70, 170.57, 169.90, 169.59, 152.55, 135.14, 130.18, 128.71, 127.11, 92.99 (d, J = 24.3Hz), 88.27 (d, J = 192.3Hz), 72.78 (d, J = 19.7Hz), 72.57, 67.62 (d, J = 7.1Hz), 61.34, 44.11, 20.75, 20.67, 20.58. HRMS (ESI) calculated C 24 H 29 N2O 10 FNa[M+Na]+547.1698, measured value 547.1703.

[0392] Example 49

[0393] Preparation of compound 3-51:

[0394]

[0395] Chloroglucinol 1-15 was prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compound 3-51 was prepared by the following steps:

[0396] 2-41 (95 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-15 (839 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:1-1:1) to give a white liquid product 3-51 (305.1 mg, 81%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3) δ7.49–7.26(m,25H),5.58(d,J=8.1Hz,1H),4.95(d,J=11.4Hz,1H),4.88(d,J=11.5Hz,1H),4.7 8–4.69(m,3H),4.65(d,J=11.4Hz,1H),4.49–4.40(m,2H),4.03(d,J=2.8Hz,1H),3.98(bs,1H),3.83–3.06(m,12H); 13 C NMR (126MHz, CDCl3) δ170.62,153.36,138.53,138.51,138.22,

[0397] 137.79, 135.30, 130.11, 128.70, 128.52, 128.51, 128.42, 128.33, 128.06, 127.93, 127.79, 127.77, 127.71, 127.65, 127.12, 96.09, 82.54, 75.26, 74.89, 73.92, 73.56, 73.17, 72.95, 67.80. HRMS (ESI) calculated value C 46 H 48 N₂O₈Na[M+Na] + 779.3307, measured value 779.3310.

[0398] Example 50

[0399] Preparation of compound 3-52:

[0400]

[0401] Chloroglucinol 1-13 was prepared according to the literature (Journal of Carbohydrate Chemistry, 1995, 14, 2, 227–236), and then compound 3-52 was prepared by the following steps:

[0402] 2-41 (95 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-13 (308 mg, 1.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:2-1:3) to give a white solid product 3-52 (245.2 mg, 97%), which was a single β-configuration. (c1.0,CHCl3); 1 HNMR (500MHz, CDCl3) δ7.38–7.28(m,5H),5.51(d,J=8.3Hz,1H),5.28–5.15(m,2H),5.03(dd,J=10.5,3.5H z,1H),3.94–3.88(m,1H),3.82–3.07(m,8H),2.09(s,3H),1.95(s,3H),1.90(s,3H),1.14(d,J=6.3Hz,3H); 13 C NMR (126MHz, CDCl3) δ 170.44, 170.32, 169.78, 169.48, 152.69, 135.02, 129.94, 128.50, 126.94, 93.77, 77.42, 77.16, 76.90, 70.77, 69.88, 67.80, 47.12, 43.87, 41.68, 20.63, 20.51, 20.44, 15.78. HRMS (ESI) calculated C 24 H 30 N2O 10 Na[M+Na]+529.1793, measured value 529.1797.

[0403] Example 51

[0404] Preparation of compound 3-53:

[0405]

[0406] Chloroglycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compounds 3-53 were then prepared by the following steps:

[0407] 2-42 (0.16 mL, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 6:1) to give a white solid product 3-53 (553.5 mg, 75%), which was a single β-configuration. (c 1.0, CHCl3); 1 HNMR(500MHz, CDCl3)δ8.16–8.08(m,1H),7.91–7.84(m,1H),7.79(d,J=8.0Hz,1H),7.56–7.42( m,4H),7.39–7.22(m,18H),7.17–7.11(m,2H),5.68(p,J=7.1Hz,1H),5.59(d,J=8.2Hz,1H),5.02 (d,J=8.0Hz,1H),4.91(d,J=10.9Hz,1H),4.86–4.74(m,4H),4.60(d,J=12.1Hz,1H),4.53(d,J=1 0.8Hz,1H),4.45(d,J=12.1Hz,1H),3.77–3.68(m,4H),3.58–3.51(m,2H),1.66(d,J=6.8Hz,3H). 13C NMR (126MHz, CDCl3) δ153.58,138.54,138.45,138.25,138.18,138.10,134.06 ,130.89,128.97,128.56,128.53,128.45,128.21,128.07,128.05,128.02,12 7.89, 127.85, 127.73, 126.68, 125.94, 125.35, 123.31, 122.49, 95.31, 84.96, 81.37, 75.91, 75.42, 75.17, 75.13, 73.62, 68.13, 46.89, 21.76. HRMS (ESI) calculated value C 47 H 47 NO7Na[M+Na] + 760.3245, measured value 760.3248.

[0408] Example 52

[0409] Preparation of compound 3-54:

[0410]

[0411] A. Synthesis of halogenated glycosides 1-17

[0412] At 0°C, 4-4 (236 mg, 0.5 mmol) was dissolved in a DMF / DCM (3 mL / 9 mL) mixed solution. A DCM solution (3 mL) containing oxaloyl chloride (200 mg, 1.5 mmol) was added to the system, and the reaction was carried out at 0°C for 30 min. The ice bath was removed, and the reaction was continued for 3 h. The reaction solution was concentrated, dissolved in EA, washed with water and saturated sodium bicarbonate, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1) to obtain colorless syrup 1-17 (234.5 mg, 96%). (c 1.0, CHCl3); 1 H NMR (500MHz, CDCl3) δ7.49–7.31(m,13H),7.25–7.19(m,2H),6.29(d,J=4.1 Hz,1H),4.97(d,J=11.0Hz,1H),4.92(d,J=10.7Hz,1H),4.83(d,J=11.1Hz,1 H),4.81–4.67(m,1H),4.65(d,J=11.9Hz,1H),4.58(d,J=11.0Hz,1H),4.54 (d,J=12.1Hz,1H),4.28–4.15(m,2H),3.89–3.81(m,2H),3.77–3.70(m,1H). 13C NMR (126MHz, CDCl3) δ138.02,137.82,137.62,128.53,128.51,128.11,128.03,128.00,127.97,127.95,91.19 (d, J=2. 1Hz), 90.51 (d, J = 222.2Hz), 80.15 (d, J = 15.8Hz), 75.61 (d, J = 8.6Hz), 75.43, 75.29 (d, J = 2.9Hz), 73.55, 73.39, 67.50. 19 F NMR (376MHz, CDCl3) δ-190.12.HRMS (ESI) calculated value [C 27 H 28 O4Cl]Na+: 493.1552. Measured value: 493.1555

[0413] B. Synthesis of Compounds 3-54

[0414] 2-42 (0.032 mL, 0.2 mmol), cesium carbonate (139 mg, 0.3 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Chloroglucinol 1-17 (282 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 7:1) to give a yellow solid product 3-54 (63.8 mg, 43%), which was in a single β configuration. (c 1.0, CHCl3); 1HNMR (500MHz, CDCl3) δ8.13(d,J=8.3Hz,1H),7.88(d,J=7.9Hz,1H),7.80(d,J=8.1Hz,1H),7.58–7.43(m,4H ),7.41–7.24(m,13H),7.19–7.12(m,2H),5.75–5.65(m,2H),5.29(d,J=7.9Hz,1H),4.82(d,J=10.8Hz,1H),4 .78(d,J=11.1Hz,1H),4.59(d,J=12.1Hz,1H),4.52(d,J=11.0Hz,1H),4.50–4.35(m,2H),3.84(dt,J=14.6, 8.8Hz,1H),3.75(t,J=9.3Hz,1H),3.71(d,J=2.6Hz,2H),3.57(dd,J=9.8,2.6Hz,1H),1.69(d,J=6.8Hz,1H); 13 C NMR (126MHz, CDCl3) δ153.38,138.31,138.05,138.01,137.95,134.07,130.83,129.01, 128.56,128.52,128.50,128.47,128.18,128.03,127.95,127.81,126.65,125.93,125.4 2,123.21,122.50,92.82 (d,J=22.0Hz),92.22 (d,J=187.5Hz),83.25 (d,J=14.9Hz),76.57 (d,J=7.0Hz),75.56,75.20 (d,J=17.1Hz),73.64,67.87,47.10,21.82.HRMS(ESI) calculated value C 40 H 40 NO6FNa[M+Na] + 672.2732, measured value 672.2739.

[0415] Example 53

[0416] Preparation of compound 3-55:

[0417]

[0418] Chloroglucinol 1-15 was prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compound 3-55 was prepared by the following steps:

[0419] 2-42 (171 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-15 (1680 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1) to give a white solid product 3-55 (317.3 mg, 43%), which was in a single β configuration. (c 0.1, CH2Cl2); 1 HNMR (600MHz, CDCl3) δ8.09–8.05(m,1H),7.87–7.83(m,1H),7.76(d,J=8.0Hz,1H),7.50–7.39(m,4H),7.38–7.20 (m,20H),5.65(p,J=7.0Hz,1H),5.55(d,J=8.1Hz,1H),5.01(d,J=8.0Hz,1H),4.91(d,J=11.6Hz,1H),4.83(d,J=1 1.3Hz,1H),4.75(d,J=11.3Hz,1H),4.72(s,2H),4.60(d,J=11.6Hz,1H),4.41(d,J=11.7Hz,1H),4.37(d,J=11.7H z,1H),3.96(d,J=2.9Hz,1H),3.89(t,J=8.9Hz,1H),3.70–3.66(m,1H),3.64–3.52(m,3H),1.64(d,J=6.8Hz,3H). 13 C NMR (151MHz, CDCl3) δ153.69,138.75,138.66,138.40,138.30,137.93,134.05,130. 90,128.92,128.55,128.46,128.44,128.37,128.32,128.18,128.08,127.92,127.8 1,127.75,127.71,126.62,125.90,125.32,123.34,122.44,95.60,82.54,78.52,75.40,74.79,73.94,73.61,73.26,73.04,68.04,46.87,29.85,21.77.HRMS(ESI) calculated value C 47 H 47NO7Na[M+Na] + 760.3245, measured value 760.3252.

[0420] Example 54

[0421] Preparation of compound 3-56:

[0422]

[0423] Chloroglucinol 1-14 was prepared according to the literature (Carbohydrate Research, 2008, 343, 17, 2989-2991), and then compounds 3-56 were prepared by the following steps:

[0424] 2-42 (32 μL, 0.2 mmol), cesium carbonate (98 mg, 0.3 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-14 (118 mg, 0.4 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2.4:1) to give a white liquid product 3-56 (48.0 mg, 51%), which was in a single α configuration. (c 1.0, CHCl3); 1 HNMR (500MHz, CDCl3) δ8.07(d,J=8.5Hz,1H),7.85(d,J=8.0Hz,1H),7.77(d,J=8.0Hz,1H),7.53(ddd ,J=8.5,6.8,1.5Hz,1H),7.51–7.46(m,2H),7.43(t,J=7.6Hz,1H),5.65(p,J=7.1Hz,1H),5.60(d,J=7 .7Hz,1H),5.41(d,J=7.7Hz,2H),5.31–5.25(m,2H),5.09(dd,J=9.8,3.5Hz,1H),3.97(dd,J=13.4,2. 8Hz,1H),3.73(dd,J=13.3,1.6Hz,1H),2.10(s,3H),2.09(s,3H),2.01(s,3H),1.64(d,J=6.8Hz,3H); 13CNMR (126MHz, CDCl3) δ 170.30, 170.04, 169.81, 153.20, 138.04, 134.00, 130.77, 128.96, 128.48, 126.64, 125.90, 125.35, 123.04, 122.40, 93.59, 70.42, 68.29, 67.64, 64.40, 46.94, 21.61, 20.94, 20.88, 20.71. HRMS (ESI) calculated value C 24 H 27 NO9Na[M+Na]+496.1578, measured value 496.1584.

[0425] Example 55

[0426] Preparation of compound 3-58:

[0427]

[0428] Chloroglucinogenic compounds 1-9 were prepared according to the literature (Angewandte Chemie-International Edition, 2012, 51, 6, 1432-1436), and compounds 3-58 were then prepared by the following steps:

[0429] 2-42 (64 μL, 0.4 mmol), cesium carbonate (196 mg, 0.6 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-9 (260 mg, 0.8 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2.5:1) to obtain a mixture containing impurities. The mixture was dissolved in 2 mL of anhydrous methanol, and K₂CO₃ (10 mg) was added. The reaction was carried out at room temperature for 30 min. The reaction was monitored by TLC until complete. The pH was adjusted to neutral by adding acidic resin, and the system was clear. The mixture was filtered through diatomaceous earth, concentrated, and subjected to column chromatography (PE:EA = 1:1 - MeOH:EA = 1:4). The product was dissolved in 1 mL of anhydrous pyridine, and 0.1 mL of acetic anhydride was added. The mixture was reacted overnight at room temperature. The reaction solution was quenched with methanol, concentrated, dissolved in dichloromethane, washed with dilute hydrochloric acid, saturated sodium bicarbonate, saturated sodium chloride, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1) to give a yellow solid product 3-95 (91.0 mg, 45%). The product was a single β configuration. (c 1.0, CHCl3);1 H NMR (500MHz, CDCl3) δ8.10(d,J=8.5Hz,1H),7.89–7.84(m,1H),7.79(d,J=7.8Hz,1H),7.55(ddd,J=8.4,6.8,1.5H z,1H),7.53–7.46(m,2H),7.45(t,J=7.6Hz,1H),5.77(dd,J=8.1,2.9Hz,1H),5.67(p,J=7.0Hz,1H),5.44–5.32(m ,2H),5.04(t,J=9.8Hz,1H),4.48–4.32(m,1H),4.29(dd,J=12.5,4.4Hz,1H),4.11(q,J=7.1Hz,1H),4.05(dd,J=1 2.5,2.2Hz,1H),3.82(ddd,J=10.1,4.3,2.2Hz,1H),2.08(s,3H),2.02(s,3H),2.01(s,3H),1.68(d,J=6.8Hz,3H). 13 CNMR (126MHz, CDCl3) δ 170.68, 170.01, 169.67, 152.80, 138.06, 137.81, 130.79, 129.04, 128.58, 126.69, 125.98, 125.40, 123.10, 122.52, 92.48 (d, J = 24.3Hz), 88.36 (d, J = 192.1Hz), 77.41, 77.16, 76.91, 72.91 (d, J = 19.2Hz), 72.50, 67.71, 61.37, 47.18, 21.70, 20.77, 20.66, 14.31. HRMS (ESI) calculated value C 25 H 28 NO9FNa[M+Na]+528.1640, measured value 528.1647.

[0430] Example 56

[0431] Preparation of compound 3-59:

[0432]

[0433] Chlorinated glycoside 1-1 was prepared according to the literature (Carbohydrate Research. 2008, 343, 2989-2991), and then compound 3-59 was prepared by the following steps:

[0434] 2-42 (80 μL, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chlorinated glycoside 1-1 (549 mg, 1.5 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1) to give a yellow liquid product 3-59 (197.4 mg, 70%), which was in a single β configuration. (c 1.0, CHCl3); 1 H NMR

[0435] (500MHz, CDCl3) δ7.43–7.31(m,1H),5.58(d,J=8.3Hz,1H),5.24(t,J=9.5Hz,1H),5.15–5.02(m,1H),4.27(dd,J=12.6,4.2H z,1H),4.06(dd,J=12.5,2.3Hz,1H),3.82(ddd,J=10.2,4.2,2.2Hz,1H),3.78–3.22(m,8H),2.03(s,3H),2.00–1.94(m,9H); 13 C NMR (126MHz, CDCl3) δ 170.64, 170.60, 170.02, 169.45, 169.35, 152.52, 135.00, 130.14, 128.65, 127.04, 93.41, 72.42, 72.34, 70.04, 67.76, 61.33, 46.93, 44.03, 41.70, 20.74, 20.64, 20.58, 20.57. HRMS (ESI) calculated C 27 H 31 NO 11 Na[M+Na]+568.1789, measured value 568.1797.

[0436] If the above experiment is repeated using iodinated glycosides 1-3 (prepared according to the method in the Polish Journal of Chemistry. 2001, 75, 6, 803-811), product 3-59 is obtained in 48% yield.

[0437] Example 57

[0438] Preparation of compound 3-60:

[0439]

[0440] Chloroglucinol 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compound 3-60 was prepared by the following steps:

[0441] 2-43 (407 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (1680 mg, 3.0 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:3) to give a white solid product 3-60 (423.8 mg, 44%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (600MHz, CDCl3): δ7.29-7.20(m,18H),7.14-7.09(m,2H),7.07-7.00(m,1H),6.74-6.65(m ,1H),5.97-5.92(m,1H),5.47(d,J=8.2Hz,1H),4.92-4.84(m,2H),4.84-4.76(m,3H),4.73-4.6 2(m,2H),4.57-4.51(m,1H),4.48(d,J=10.8Hz,1H),4.41(d,J=12.0Hz,1H),4.28-3.82(m,5H), 3.73-3.59(m,4H),3.58-3.53(m,1H),3.52-3.45(m,1H),3.00-2.88(m,2H),2.76-2.64(m,2H); 13C NMR (151MHz, CDCl3): δ170.29, 169.59, 169.35, 161.98, 156.14 (dd, J = 243.3, 9.1Hz), 153.88, 15 3.80,150.33,149.61,148.93(dt,J=251.5,13.5Hz),146.74(dd,J=243.8,12.6Hz),144.20-142. 93(m),138.37,138.33,138.10,137.99,137.97,137.93,137.81,137.75,131.30,129.62,128.8 6,128.83,128.81,128.67,128.53,128.45,128.41,128.30,128.15,128.04,127.98,127.93,127 .91,127.86,127.83,127.79,127.76,127.74,127.67,121.43-120.94(m),119.53-118.87(m),1 17.42,117.35,115.63,115.56,105.45(dd,J=28.6,20.7Hz),95.39,95.36,84.65,80.97,80.84, 77.31, 77.27, 75.78, 75.12, 75.03, 74.77, 74.74, 73.43, 69.13, 68.45, 68.39, 49.16, 48.93, 43.60, 43.19, 42.47, 41.56, 39.07, 37.91, 37.78, 36.47, 36.13, 35.33, 32.88, 32.54. HRMS (ESI) calculated value C 51 H 49 N5O8F6Na[M+Na] + 996.3378, measured value 996.3377.

[0442] Example 58

[0443] Preparation of compound 3-61:

[0444]

[0445] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-61 was prepared according to the following method.

[0446] 2-44 (215 mg, 1.10 mmol), cesium carbonate (537.6 mg, 1.65 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (904.7 mg, 2.20 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1-1:1) to give a white solid product 3-61 (611 mg, 97%), which was a single β-configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ7.15–7.06(m,2H),7.03–6.99(m,1H),5.69–5.66(m,1H),5.32–5.24 (m,1H),5.24–5.18(m,1H),5.16–5.11(m,1H),4.36–4.25(m,1H),4.13–4.09(m,1H),3.87– 3.75(m,2H),3.72–3.53(m,1.50H),3.46–3.24(m,1.36H),3.16–2.97(m,1.52H),2.95–2.8 8(m,0.44H),2.87–2.75(m,1H),2.09–2.06(m,3H),2.05–1.99(m,9H),1.27(d,J=7.2Hz,3H; 13 C NMR (151MHz, CDCl3): δ170.77,170.73,170.20,170.18,169.61,169.56,169.44,153.54,146.1 6,146.07,137.64,137.09,132.57,132.55,132.01,131.87,128.52,126.55,126.48,93.55,93 .37,72.89,72.74,72.65,72.48,70.37,70.26,68.16,68.09,61.62,61.58,51.76,51.08,47.11,46.83,41.36,40.95,36.17,35.26,20.88,20.85,20.76,20.73,18.15,17.41.HRMS(ESI) calculated value C 26 H 32 ClNO11 Na[M+Na]+592.1560, measured value 592.1556.

[0447] Example 59

[0448] Preparation of compound 3-62:

[0449]

[0450] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-62 was prepared according to the following method.

[0451] 2-45 (200 mg, 0.48 mmol), cesium carbonate (234.6 mg, 0.72 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (394.8 mg, 0.96 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and column-chromatographically analyzed (PE:EA = 4:1-2:1-1:1). The resulting mixture was then column-chromatographically analyzed again (DCM:MeOH = 200:1-100:1) to give product 3-62 (273 mg, 72%), which was a single β-configuration. [α] 2 D 5 = -6.2 (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ7.79–7.53(m,2H),7.12–7.02(m,1H),6.98–6.87(m,1H),5.69–5.39(m,1H),5.32–4.94(m,3H),4. 65–4.04(m,8H),4.02–3.57(m,4H),3.13–2.78(m,1H),2.14–1.98(m,11.75H),1.94–1.82(m,1.67H),1.79–1.60(m,6H); 13C NMR (151MHz, CDCl3): δ170.73,170.22,169.59,169.36,164.22,153.79,153.55,153.12,153.05,150.53,12 3.2(m),120.73,117.51,117.18,115.74,115.54,115.37,93.46,72.64,72.51,70.24,70.03,69.65,68.40, 68.04, 67.73, 67.52, 67.29, 66.4 (m), 62.01, 61.58, 61.39, 51.25, 50.91, 40.71, 40.24, 39.86, 39.55, 39.21, 39.04, 29.84, 29.41, 26.44, 25.54, 25.17, 24.85, 20.85, 20.70, 20.40, 19.29, 19.17, 18.68. HRMS (ESI) calculated value C 32 H 38 F6N2O 14 Na[M+Na] + 811.2115, measured value 811.2119.

[0452] Example 60

[0453] Preparation of compound 3-63:

[0454]

[0455] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-63 were prepared according to the following method.

[0456] 2-46 (100 mg, 0.584 mmol), cesium carbonate (285.4 mg, 0.876 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Bromoglycoside 1-2 (480.3 mg, 1.168 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1). The resulting mixture was added to methanol and allowed to stand overnight. Filtering yielded a white solid product 3-63 (294 mg, 92%), which was a single β-configuration. (c 0.1, CH2Cl2); 1H NMR (600MHz, CDCl3): δ7.31–7.13(m,3.63H),7.02(d,J=7.5Hz,0.38H),5.86–5.73(m,1.62H), 5.64(t,J=8.0Hz,0.38H),5.31–5.09(m,3H),4.39–4.32(m,1H),4.19–4.08(m,1.69H),4.06–4 .00(m,0.39H),3.91–3.84(m,1H),3.56–3.49(m,0.36H),3.39–3.32(m,0.57H),3.11–3.00(m, 1H),2.90–2.82(m,1H),2.53–2.42(m,1H),2.36–2.18(m,1H),2.11(s,3H),2.05–1.97(m,9H); 13 C NMR (151MHz, CDCl3): δ170.81,170.31,170.22,169.59,169.57,169.31,169.26,153.80,153.69,144.26 ,143.79,140.26,140.05,128.50,128.47,126.98,126.78,125.37,125.26,124.53,123.92,93.67,93.5 4,80.56,80.05,73.13,72.88,72.72,72.70,71.26,70.81,70.24,70.17,68.02,67.98,62.52,62.22,61.61,61.57,33.46,32.72,30.46,30.29,30.18,29.79,20.93,20.90,20.74,20.72,20.65.HRMS(ESI) calculated value C 27 H 31 NO 11 Na[M+Na] + 568.1788, measured value 568.1789.

[0457] Example 61

[0458] Preparation of compound 3-64:

[0459]

[0460] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-64 were prepared according to the following method.

[0461] 2-44 (30 mg, 0.084 mmol), potassium carbonate (17.4 mg, 0.126 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (69.1 mg, 0.168 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1 - DCM:MeOH = 10:1) to give product 3-64 (27 mg, 46%), which was a single β-configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ9.13–8.99(m,1H),8.53–8.48(m,1H),8.31(d,J=7.0Hz,1H),7.96–7.77(m ,3H),7.50–7.37(m,2H),7.30–7.24(m,1H),6.07(d,J=3.6Hz,1H),5.72(d,J=8.2Hz,0.49H),5.65 (d,J=8.3Hz,0.48H),5.34–5.25(m,1H),5.23–5.07(m,2H),4.41–4.06(m,4H),3.90–3.82(m,1H) ,2.90–2.77(m,2.44H),2.68–2.60(m,0.63H),2.11(s,3H),2.08–2.00(m,9H),1.93–1.67(m,4H); 13C NMR (151MHz, CDCl3): δ170.79,170.76,170.22,170.17,169.61,169.53,167.24,152.98,152.39,147.05, 143.60,143.16,138.78,138.75,131.09,128.54,128.52,125.19,123.79,122.67,121.81,121.77,121.4 3,121.19,93.55,93.44,72.79,72.63,72.60,70.56,70.26,68.08,61.61,51.23,50.64,44.66,44.54,42.44,41.90,31.49,30.78,29.83,29.79,25.38,25.32,20.91,20.85,20.79,20.74,20.72.HRMS(ESI) calculated value C 34 H 38 N4O 12 Na[M+Na] + 717.2381, measured value 717.2378.

[0462] Example 62

[0463] Preparation of compound 3-65:

[0464]

[0465] Chloroglucinogenic compounds 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compounds 3-65 were then prepared by the following steps:

[0466] 2-48 (100 mg, 0.56 mmol), cesium carbonate (365 mg, 1.12 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (933.7 mg, 1.67 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 10:1-8:1) to give a white solid product 3-65 (278 mg, 66%), which was a single β-configuration. (c0.1,CH2Cl2); 1H NMR (600MHz, CDCl3): δ7.35–7.21(m,18H),7.16–7.11(m,2H),7.01–6.88(m,3 H),5.61–5.55(m,1H),5.18(d,J=8.4Hz,0.44H),5.09(d,J=8.2Hz,0.56H),4.9 4–4.70(m,5H),4.67–4.60(m,1H),4.56–4.45(m,2H),4.15–4.03(m,1H),3.81 –3.69(m,6H),3.60–3.53(m,2H),2.26(s,3H),2.21(s,3H),1.45–1.38(m,3H); 13 C NMR (151MHz, CDCl3): δ155.02,153.94,153.83,138.60,138.57,138.39,138.23,138.11,130.97,1 30.85,129.11,128.55,128.53,128.49,128.45,128.28,128.09,128.04,128.02,127.89,127.82, 127.80, 124.25, 124.23, 95.46, 95.24, 85.05, 84.89, 81.19, 75.88, 75.38, 75.36, 75.13, 74.98, 74.03, 73.83, 73.68, 73.62, 68.24, 68.20, 47.52, 47.50, 18.05, 18.01, 16.44, 16.29. HRMS (ESI) calculated value C 46 H 51 NO8Na[M+Na] + 768.3509, measured value 768.3507.

[0467] Example 63

[0468] Preparation of compound 3-66:

[0469]

[0470] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-66 was prepared according to the following method.

[0471] 2-49 (118 mg, 0.3 mmol), cesium carbonate (146.6 mg, 0.45 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (246.7 mg, 0.6 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1) to give product 3-66 (145 mg, 66%), which was a single β-configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ8.17 (d, J=8.4Hz, 0.30H), 8.05 (d, J=8.3Hz, 1H), 7.90–7.85 (m, 2H), 7.84–7.7 8(m,2H),7.76(d,J=8.2Hz,0.33H),7.57–7.47(m,4.24H),7.45–7.18(m,8.64H),6.97(s,1H),6.91( d,J=7.7Hz,1H),6.88–6.82(m,1H),6.64(d,J=0.6Hz,0.58H),6.18(q,J=6.9Hz,1H),5.98(q,J=6.8H z,0.47H),5.84(d,J=8.0Hz,0.51H),5.81(d,J=8.3Hz,1H),5.57(dt,J=4.3,0.9Hz,0.58H),5.38–5.2 7(m,2.07H),5.27–5.19(m,1.16H),5.17–5.08(m,2.14H),4.45–4.40(m,0.60H),4.40–4.28(m,2.34 H),4.23(dd,J=12.1,3.5Hz,0.63H),4.20–4.08(m,1.66H),3.92–3.87(m,1.48H),3.10(td,J=9.6,9. 1,4.8Hz,0.40H),2.95–2.80(m,2.43H),2.77–2.54(m,1.08H),2.23–2.15(m,3.12H),2.11–2.09(m, 7.74H),2.05–2.01(m,14.81H),1.98(s,2.86H),1.67(d,J=6.9Hz,1.53H),1.63(d,J=6.9Hz,3.47H); 13C NMR (151MHz, CDCl3): δ170.75,170.63,170.26,170.23,169.72,169.62,169.60,169.46, 153.88,153.63,142.36,142.30,139.41,135.18,134.97,134.11,133.81,132.23,132.1 1,131.89,131.72,131.50,131.39,130.8–130.2(m),129.21,129.17,129.15,128.92,12 8.81,128.68,128.64,127.54,127.03,126.77,126.22,126.11,125.99,125.85,125.51,

[0472] 125.21,125.18,125.1–124.5(m),123.77,123.42,123.10,122.8–122.6(m),93.53 ,93.42,77.37,77.16,76.95,74.28,73.11,72.94,72.60,72.44,70.50,70.44,68.2 3,67.62,66.48,61.72,61.68,61.09,51.43,50.90,43.37,42.20,33.50,32.95,30.99,30.02,20.90,20.86,20.83,20.73,20.70,20.64,18.04,17.25.HRMS(ESI) calculated value C 37 H 40 F3NO 11 Na[M+Na] + 754.2451, measured value 754.2446.

[0473] Example 64

[0474] Preparation of compound 3-67:

[0475]

[0476] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-67 were prepared according to the following method.

[0477] 2-50 (70 mg, 0.2 mmol), cesium carbonate (97.8 mg, 0.3 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (164.5 mg, 0.4 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 8:1-4:1-2:1-1:1) to give product 3-67 (99 mg, 69%), which was a single β-configuration. (c0.1,CH2Cl2); 1 ¹H NMR (600MHz, CDCl₃): (a mixture of a pair of diastereomers and rotational isomers) δ 7.09–6.97 (m, 2H), 6.93–6.80 (m, 2H), 6.51–6.39 (m, 1H), 5.69–5.64 (m, 0.21H), 5.61–5.49 (m, 0.86H), 5.31–5.18 (m, 1.48H), 5.17–5.06 (m, 1.62H), 4.52–4.44 (m, 0.61H), 4.41–4.22 (m, 1.65H), 4.21–4.05 (m, 1.89H), 3.99 (dd, J = 14.7, 6.5Hz, 0.24H), 3.86–3.76 (m, 7.2H). 2H),3.72–3.67(m,2.90H),3.59–3.48(m,0.92H),3.48–3.39(m,1.13H),3.35 (dt,J=15.6,4.3Hz,0.21H),3.28(dt,J=15.4,4.1Hz,0.52H),3.16(td,J=11.2 ,5.6Hz,0.22H),3.11–3.03(m,0.63H),3.00–2.92(m,0.23H),2.12–2.06(m,2. 98H),2.06–1.98(m,7.65H),1.93(s,0.63H),1.84(s,0.45H),1.82(s,1.05H); 13C NMR (151MHz, CDCl3): (a mixture of a pair of diastereomers and rotational isomers) δ 170.87, 170.80, 170.69, 170.28, 170.23, 170.21, 170.15, 169.76, 169.68, 169.65, 169.57, 169.48, 169.36, 169.31, 158.60, 158.58, 158.50, 153.88, 153.86, 153.82, 153.46, 152.05, 152 .02,151.97,151.84,144.23,144.20,144.14,144.02,138.31,137.79,137.64,137.60,134.34,134.20,134.14,133.22,129.22,129.19,129.04,129.01,128.88,128.81,128.76,128.69,128.09,128.07,128.02,114.32,114.10,113 .99,113.73,113.61,113.50,93.52,93.37,93.32,72.87,72.85,72.69,72.63,72.58,72.57,72.54,71.15,70.44,70.36,70.09,70.00,69.94,68.57,68.54,68.15,68.10,68.06,67.98,67.48,62.06,61.70,61.67,61.62,61.52,60. 62,60.56,56.08,56.05,55.96,55.41,55.38,50.96,50.77,50.47,50.27,49.68,49.46,49.40,49.05,46.17,45.87,45.79,29.19,28.67,28.22,27.95,20.90,20.87,20.83,20.81,20.77,20.73,20.71,20.47,20.27.HRMS(ESI) calculated value C 34 H 44 ClN2O 14 [M+H] + 739.2480, measured value 739.2476.

[0478] Example 65

[0479] Preparation of compound 3-68:

[0480]

[0481] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-68 was prepared according to the following method.

[0482] 2-51 (60 mg, 0.2 mmol), cesium carbonate (97.8 mg, 0.3 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (164.5 mg, 0.4 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1) to give product 3-68 (132 mg, 98%), which was a single β-configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3) δ7.35(d,J=7.8Hz,1H),7.17–7.14(m,1H),7.07(td,J=7.5,1.5Hz,1H),7.05–6.98(m,2H),6.89(td,J=7.6,1 .3Hz,1H),6.53(dd,J=7.9,1.4Hz,1H),5.66(d,J=8.3Hz,1H),5.29(t,J=9.5Hz,1H),5.20(dd,J=9.7,8.3Hz,1H),5.15(t,J=9.7H z,1H),4.34(dd,J=12.6,4.2Hz,1H),4.14(dd,J=12.6,2.2Hz,1H),3.87(ddd,J=10.1,4.2,2.2Hz,1H),3.74–3.62(m,3H),3.62–3 .54(m,1H),3.10–3.00(m,3H),2.99–2.92(m,1H),2.36(s,3H),2.31(s,3H),2.10(s,3H),2.06(s,3H),2.04(s,3H),2.03(s,3H); 13CNMR (151MHz, CDCl3) δ 170.82, 170.23, 169.62, 169.52, 152.90, 148.64, 142.47, 139.49, 136.24, 134.81, 131.88, 128.00, 127.73, 126.51, 125.70, 125.01, 120.01, 93.50, 72.76, 72.64, 70.25, 68.09, 61.61, 51.56, 51.34, 44.73, 44.56, 21.33, 20.91, 20.80, 20.76, 20.73. HRMS (ESI) calculated value C 33 H 41 N2O 11 S[M+H] + 673.2432, measured value 673.2426.

[0483] Example 66

[0484] Preparation of compound 3-69:

[0485]

[0486] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-69 were prepared according to the following method.

[0487] 2-52 (100 mg, 0.18 mmol), cesium carbonate (83.1 mg, 0.255 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (139.8 mg, 0.34 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-1:1) to give product 3-69 (135.8 mg, 81%), which was a single β-configuration. (c 0.1, CH2Cl2); 1H NMR (600MHz, CDCl3): δ9.53–9.50(m,1H),8.57(d,J=8.4Hz,1H),8.15(s,1H),8.02(s,1H),7.95–7.90(m,1H),7.64–7.59(m,1H),7. 56(s,1H),7.29–7.23(m,1H),6.71(s,0.51H),6.65(s,0.49H),5.69–5.61(m,1H),5.32–5.26(m,1H),5.20(t,J=9.0Hz,1H),5.15(t ,J=9.7Hz,1H),4.60–4.46(m,1H),4.39–4.30(m,2H),4.25–4.10(m,2H),3.90–3.85(m,1H),3.26(hept,J=6.9Hz,1H),3.00–2.73(m ,3H),2.16(s,3H),2.10(s,3H),2.06–2.00(m,9H),1.82–1.75(m,2H),1.69–1.61(m,2H),1.39–1.34(m,6H),1.32(d,J=6.9Hz,6H); 13 CNMR (151MHz, CDCl3): δ170.79,170.74,170.22,169.62,169.54,169.34,157.51,155.49,155.38,152.85,152.73,144.91,1 44.84,138.58,136.77,136.68,134.76,131.43,128.05,127.94,127.19,126.90,125.08,123.81,123.30,120.97,120.87,11 0.87,106.00,93.56,93.48,72.78,72.74,72.67,72.62,71.84,71.76,70.39,70.29,68.07,61.63,61.60,55.60,45.32,45.16,45.07,44.87,38.12,38.05,32.98,32.46,32.26,32.19,22.38,20.90,20.79,20.75,20.73,19.07,15.50.HRMS(ESI) calculated value C 43 H 55 ClN5O 14 S[M+H] + 932.3156, measured value 932.3149.

[0488] Example 67

[0489] Preparation of compound 3-70:

[0490]

[0491] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-70 was prepared according to the following method.

[0492] 2-53 (150 mg, 0.4 mmol), cesium carbonate (195.5 mg, 0.6 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (329.0 mg, 0.8 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1) to give product 3-70 (190 mg, 67%), which was a single β-configuration. (c 0.1, CH2Cl2); 1 H NMR (600MHz, CDCl3): δ7.17–7.06(m,2H),7.01–6.94(m,2H),6.66–6.60(m,1H),6.42(d,J=2.5Hz,0.44H),6.34 (d,J=2.5Hz,0.53H),6.19–6.10(m,1H),5.91–5.86(m,2H),5.70–5.63(m,1H),5.34–5.25(m,1H),5.24–5.10(m, 2H),4.53–4.44(m,0.55H),4.38–4.28(m,2H),4.23–4.09(m,1.69H),3.90–3.85(m,1H),3.66–3.58(m,1H),3.4 8–3.38(m,1H),2.98–2.84(m,2H),2.76–2.68(m,1H),2.18–1.99(m,12H),1.89–1.74(m,1H),1.56–1.48(m,2H); 13C NMR (151MHz, CDCl3): δ170.81, 170.26, 170.23, 169.62, 169.40, 169.37, 161.82 (d, J = 245.1Hz), 154.24, 152.91, 152.72, 1 48.33,141.95,141.92,138.69,128.92(d,J=7.9Hz),128.79(d,J=7.9Hz),115.79(d,J=21.3Hz),115.74(d,J=21.3Hz),10 8.00, 105.86, 105.68, 101.28, 98.35, 98.12, 93.64, 93.53, 72.88, 72.74, 72.65, 70.39, 70.21, 68.61, 68.56, 68.14, 68.10, 61.65, 47.60, 47.30, 45.01, 44.86, 43.88, 43.80, 41.84, 34.16, 33.49, 20.93, 20.90, 20.79, 20.76, 20.74. HRMS (ESI) calculated value C 34 H 38 FNO 14 Na[M+Na] + 726.2173, measured value 726.2169.

[0493] Example 68

[0494] Preparation of compound 3-71:

[0495]

[0496] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-71 was prepared according to the following method.

[0497] 2-54 (43 mg, 0.1 mmol), cesium carbonate (48.9 mg, 0.15 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (82.3 mg, 0.2 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 4:1-2:1) to give product 3-71 (44.6 mg, 58%), which was a single β-configuration. (c 0.1, CH2Cl2); 1H NMR(600MHz,CDCl3):δ8.07(s,1H),7.47–7.33(m,2H),7.26–7.21(m,2H),7.05–7.01(m,1H),7.00(d,J=2.2Hz,0.54H),6.96(d,J=2.2Hz,0.48H),6.92–6.83(m,1.54H),6.82–6.76(m,1.48H),6.74(t,J=2.1Hz,0.54H),6.65(t,J=2.1Hz,0.49H),6.17–5.93(m,1H),5.76(d,J=8.3Hz,0.52H),5.73(d,J=8.4Hz,0.48H),5.34–5.06(m,3.54H),4.49(d,J=16.0Hz,0.50H),4.40–4.09(m,6.26H),3.92–3.84(m,1H),3.72–3.65(m,0.47H),3.51–3.33(m,1.49H),3.10–2.92(m,1H),2.92–2.80(m,1H),2.13–2.07(m,4.54H),2.07–2.01(m,7.36H); 13C NMR (151MHz, CDCl3): δ170.85,170.24,169.64,169.60,169.57,169.34,160.19(d,J=237.9Hz ),157.74,154.44,153.75,139.44,139.31,136.30(d,J=12.5Hz),136.27(d,J=12.5Hz),130.1 0,130.06,124.08,123.99,122.72,122.70,122.37,122.35,122.08,121.34,119.46(d,J=30.6 Hz),119.40(d,J=30.6Hz),114.62,113.98,113.66,113.39,112.93,112.71,109.17(tt,J=249 .6, 34.0Hz), 108.42 (d, J = 24.4Hz), 108.39 (d, J = 24.3Hz), 97.68 (d, J = 25.8Hz), 97.63 (d, J = 26. 2Hz),93.56,93.49,77.37,77.16,76.95,72.97,72.92,72.71,72.69,71.15,70.46,70.14,69. 94, 68.57, 68.54, 68.12, 68.06, 67.49, 65.29 (t, J = 29.5 Hz), 61.57, 61.53, 51.40, 50.82, 48.37, 47.58, 29.85, 24.29, 23.48, 20.89, 20.87, 20.84, 20.77, 20.74, 20.71, 20.43. HRMS (ESI) calculated value C 35 H 37 F5N2O 12 Na[M+Na] + 795.2161, measured value 795.2159.

[0498] Example 69

[0499] Preparation of compound 3-72:

[0500]

[0501] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-72 was prepared according to the following method.

[0502] 2-55 (95 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (226 mg, 0.55 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:4) to give a yellow solid product 3-72 (143.0 mg, 51%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3): δ7.32–7.17(m,1H),6.43–6.37(m,1H),6.08–6.02(m,1H),5.45–5.39(m,1H),5.22(t,J=9.5Hz,0.77H),5.19– 5.10(m,1H),5.07(t,J=9.7Hz,0.76H),5.01–4.95(m,0.42H),4.31(d,J=13.3Hz,0.21H),4.26(dd,J=12.5,4.2Hz,0.79H),4.22–4.1 3(m,1.88H),4.13–4.03(m,1.49H),3.95(dd,J=12.3,2.2Hz,0.22H),3.91–3.79(m,1.79H),3.75(ddd,J=10.1,4.3,2.2Hz,0.78H), 3.72–3.66(m,0.21H),3.18–2.99(m,3H),2.53–2.44(m,1H),2.16(s,2.36H),2.05(s,2.45H),2.02–1.96(m,8H),1.95–1.90(m,1H); 13C NMR (126MHz, CDCl3): δ170.73,170.37,170.05,169.60,163.29,152.79,148.44, 139.07,117.78,117.60,105.83,105.64,93.43,93.07,72.73,72.46,72.44,72. 31,70.10,69.68,67.97,61.77,61.46,51.33,51.11,50.58,50.35,48.84,41.10,34.42,34.36,27.16,25.95,25.81,20.85,20.80,20.74,20.69.HRMS(ESI) calculated value C 26 H 32 N2O 12 Na[M+Na] + 587.1847, measured value 587.1842.

[0503] Example 70

[0504] Preparation of compound 3-73:

[0505]

[0506] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-73 were prepared according to the following method.

[0507] 2-56 (21 mg, 0.1 mmol), potassium carbonate (21 mg, 0.15 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated twice to remove CO2, and then 1.5 mL of DMSO was added. The reaction was allowed to proceed at room temperature for 2 h. Bromoglycoside 1-2 (123 mg, 0.3 mmol) was dissolved in 1.5 mL of DMSO and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with 10 mL of water, washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1–1:4) to give a yellow liquid product 3-73 (50.9 mg, 87%), which was in a single β configuration. (c1.0,CHCl3); 1H NMR (500MHz, CDCl3): δ8.80–8.62(m,2H),7.93–7.70(m,2H),5.35(d,J=8.2Hz,0 .31H),5.27(d,J=8.1Hz,0.68H),5.16–4.91(m,2.72H),4.23(dd,J=12.5,4.2Hz ,0.73H),4.13–3.89(m,3.33H),3.75–3.64(m,1H),3.58(d,J=10.3Hz,0.30H),3 .52–3.37(m,2.44H),3.36–3.22(m,1H),2.46–2.36(m,1H),2.15–1.84(m,12H); 13 C NMR (126MHz, CDCl3): δ170.64,170.59,170.07,169.98,169.48,169.43,169.35,169.27,154.13,153.6 5,148.43,148.21,147.97,147.84,144.15,144.03,143.46,143.44,143.41,143.31,122.75,122.67,12 2.58, 122.08, 93.19, 92.99, 72.63, 72.40, 72.20, 70.14, 69.74, 67.94, 67.91, 61.46, 61.32, 50.05, 49.94, 49.68, 41.09, 40.86, 39.76, 39.71, 39.69, 39.62, 20.78, 20.72, 20.63, 20.59, 20.37. HRMS (ESI) calculated value C 28 H 32 N3O 11 [M+H] + 586.2031, measured value 586.2035.

[0508] Example 71

[0509] Preparation of compound 3-74:

[0510]

[0511] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-74 were prepared according to the following method.

[0512] 2-57 (156 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (226 mg, 0.55 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:4) to give a white solid product 3-74 (147.9 mg, 43%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (600MHz, CDCl3): δ8.40 (d, J=4.8Hz, 1H), 7.49–7.41 (m, 1H), 7.20–7.05 (m, 4H), 5.73 –5.58(m,1H),5.38–5.23(m,1H),5.22–5.06(m,2H),4.36–4.27(m,1H),4.15–4.06(m,1H ),3.89–3.65(m,3H),3.41–3.29(m,2H),3.25–3.10(m,2H),2.94–2.71(m,2H),2.61–2.2 0(m,4H),2.10(s,1.31H),2.07–2.04(m,3.48H),2.03–1.99(m,6.41H),1.97(s,1.29H); 13C NMR (151MHz, CDCl3): δ170.80,170.75,170.18,169.58,169.55,169.49,169.41,169.35,156.76,152.76,152.72,152.66 ,152.61,146.73,139.58,137.90,137.56,136.82,134.91,133.55,133.27,130.62,130.53,129.17,129.14,129.12,126 .44,122.57,93.47,72.75,72.73,72.70,72.60,70.30,70.27,70.25,70.09,68.06,68.04,61.58,61.55,45.18,45.12,45.07,45.04,31.73,31.62,30.73,30.65,30.54,30.46,30.38,30.24,20.90,20.87,20.78,20.73,20.71.HRMS(ESI) calculated value C 34 H 38 N2O 11 [M+H] + 685.2159, measured value 685.2162.

[0513] Example 72

[0514] Preparation of compound 3-75:

[0515]

[0516] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-75 was prepared according to the following method.

[0517] 2-58 (152 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (226 mg, 0.55 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 3:1) to give a brown liquid product 3-75 (223.7 mg, 70%), which was a single β-configuration. (c 1.0, CHCl3); 1H NMR (600MHz, CDCl3): δ7.17–7.01(m,6H),6.96–6.88(m,2H),5.63–5.57(m,1H),5.28–5 .22(m,1H),5.18–5.04(m,2H),4.33–4.25(m,1H),4.11–4.06(m,1H),3.89–3.65(m,3H) ,3.32–3.27(m,1H),3.27–3.22(m,1H),3.18–3.12(m,4H),2.77(s,1.47H),2.72(s,1.5 3H),2.08–2.05(m,3H),2.04–1.96(m,9H),1.84–1.76(m,1.52H),1.74–1.67(m,0.65H); 13 C NMR (151MHz, CDCl3): δ170.77,170.20,170.19,169.60,169.57,169.46,169.39,153.76,153.75, 148.11,148.09,134.38,134.35,130.02,126.60,126.56,122.84,122.81,119.96,119.93,93.25 ,72.93,72.82,72.51,72.44,70.36,70.30,68.15,68.04,68.00,61.78,61.60,47.93,47.69,47.49,47.06,35.09,34.27,32.28,32.25,26.48,26.00,20.88,20.86,20.73,20.71.HRMS(ESI) calculated value C 33 H 40 N2O 12 Na[M+Na] + 663.2524, measured value 663.2527.

[0518] Example 73

[0519] Preparation of compound 3-76:

[0520]

[0521] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-76 was prepared according to the following method.

[0522] 2-59 (291 mg, 1.0 mmol), potassium carbonate (208 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (452 ​​mg, 1.1 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:4) to give a white solid product 3-76 (422.4 mg, 64%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (600MHz, CDCl3): δ9.32 (s, 1H), 8.66 (t, J = 6.5Hz, 1H), 8.38–8.32 (m, 1H), 8.29 (ddd ,J=7.4,4.9,1.2Hz,1H),8.18(dq,J=8.2,1.3Hz,1H),7.66(ddd,J=8.2,7.3,5.1Hz,1H) ,5.63–5.58(m,1H),5.26–5.20(m,1H),5.16–5.03(m,2H),4.27–4.20(m,1H),4.11–4.0 5(m,1H),3.89–3.77(m,1H),3.74–3.57(m,2H),3.56–3.20(m,6H),2.05–1.81(m,14H); 13 C NMR (151MHz, CDCl3): δ170.57,170.04,170.02,169.55,169.49,169.40,153.41,153.36,153.00,14 5.27,134.20,134.18,133.73,133.71,133.13,133.10,131.55,129.25,125.96,125.94,117.40,11 7.37, 93.34, 93.31, 72.66, 72.61, 72.50, 72.47, 72.41, 70.15, 70.12, 67.97, 61.46, 49.61, 49.54, 49.15, 49.13, 47.49, 47.35, 46.41, 46.10, 28.55, 28.02, 20.75, 20.69, 20.66, 20.62. HRMS(ESI) calculated value C 29 H 35 N3O 13 Na[M+Na]+ 688.1783, measured value 688.1788.

[0523] Example 74

[0524] Preparation of compound 3-77:

[0525]

[0526] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-77 was prepared according to the following method.

[0527] 2-60 (289 mg, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (822 mg, 2.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a white solid product 3-77 (450.8 mg, 68%), which was a single β-configuration. (c 1.0, CHCl3); 1 HNMR (600MHz, CDCl3): δ7.14(s,1H),6.84(s,2H),5.64–5.57(m,1H),5.28–5 .21(m,1H),5.18–5.07(m,2H),4.33–4.25(m,1H),4.20–3.99(m,3H),3.94(s ,3H),3.88(s,3H),3.86–3.81(m,1H),3.26–3.19(m,1H),2.88–2.72(m,2H), 2.70–2.63(m,2H),2.10–1.96(m,12H),1.92–1.64(m,5H),1.40–1.27(m,2H); 13C NMR (151MHz, CDCl3): δ207.46,170.76,170.17,169.58,169.47,169.44,155.70,155.67,152.80,152.56,149.6 1,148.70,130.98,129.24,128.88,107.43,104.48,93.35,93.32,72.78,72.67,72.50,70.22,70.20,68.05,61. 59,61.56,56.32,56.19,45.09,45.07,44.52,44.49,44.41,44.20,38.62,38.57,34.30,33.51,33.49,33.26,32.95,32.56,32.40,32.18,31.99,31.73,31.60,31.39,31.33,20.84,20.83,20.71,20.68,20.66.HRMS(ESI) calculated value C 32 H 41 NO 14 Na[M+Na] + 686.2419, measured value 686.2420.

[0528] Example 75

[0529] Preparation of compound 3-78:

[0530]

[0531] Chloroglycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and compounds 3-78 were then prepared by the following steps:

[0532] 2-48 (24 mg, 0.1 mmol), cesium carbonate (49 mg, 0.15 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Chloroglucinol 1-4 (168 mg, 0.3 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1–1:3) to give a white solid product 3-78 (50.0 mg, 56%), which was in a single β configuration. [α] 2 D 5=53.3 (c0.5, CHCl3); 1 H NMR (500MHz, CDCl3) δ8.07(bs,1H),7.48(bs,1H),7.42–7.20(m,19H),7.17–7.12(m,2H),6.32(bs,1H),5.67(d,J=8.1Hz,1H),4.92(d,J=11.0Hz ,1H),4.89–4.74(m,4H),4.55–4.50(m,2H),4.43(d,J=12.0Hz,1H),3.8 3–3.56(m,7H),3.41–3.33(m,1H),3.23–3.12(m,1H),2.09–1.86(m,7H); 13 C NMR (126MHz, CDCl3) δ 168.06, 157.64, 153.97, 138.42, 138.28, 137.95, 137.75, 128.60, 128.55, 128.49, 128.08, 128.06, 127.97, 127.95, 127.89, 127.86, 127.75, 95.48, 84.87, 81.34, 77.26, 75.79, 75.46, 75.17, 73.54, 68.16, 63.22, 48.92, 39.77, 25.41, 22.97. HRMS (ESI) calculated C 48 H 50 N4O8Na[M+Na] + 833.3521, measured value 833.3520.

[0533] Example 76

[0534] Preparation of compound 3-79:

[0535]

[0536] Chloroglycosides 1-4 were prepared according to the literature (Org. Biomol. Chem. 2018, 16, 9133-9137), and then compounds 3-79 were prepared by the following steps:

[0537] 2-62 (75 mg, 0.2 mmol), cesium carbonate (98 mg, 0.3 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 1-4 (335 mg, 0.6 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:4) to give a yellow solid product 3-79 (141.3 mg, 75%), which was a single β-configuration. (c0.5,CHCl3); 1 H NMR (500MHz, CDCl3): δ8.63 (t, J=6.0Hz, 1.12H), 8.59–8.40 (m, 2.44H), 8.35– 8.29(m,1.19H),8.19(d,J=4.8Hz,1.15H),7.98(d,J=2.0Hz,1H),7.81(d,J=7 .6Hz,1H),7.78–7.69(m,0.34H),7.46(dd,J=8.0,1.9Hz,1.11H),7.37–7.19( m,23.22H),7.19–7.11(m,3.39H),7.08(d,J=8.1Hz,1.23H),6.59(dd,J=7.6,4 .8Hz,1H),6.55–6.49(m,0.14H),5.87(d,J=7.7Hz,0.15H),5.71(d,J=8.1Hz, 1H),4.91(d,J=11.0Hz,1.20H),4.88–4.78(m,4.87H),4.73(t,J=4.8Hz,2.15 H),4.67–4.50(m,3H),4.46(d,J=11.9Hz,1.31H),3.90–3.71(m,6.55H),3.64 (d,J=8.5Hz,2.30H),3.56(d,J=10.6Hz,1H),1.27(s,4.20H),1.25(s,3.19H); 13 C NMR (126MHz, CDCl3) δ166.78,157.87,152.10,151.12,150.12,149.12,141.45,138.47,

[0538] 138.09, 138.07, 137.73, 137.26, 136.99, 135.84, 128.53, 128.50, 128.44, 128.33, 128.17, 127.96, 127.92, 127.89, 127.86, 127.79, 127.74, 122.51, 122.36 ,116.49,111.69,110.45,108.27,95.46,84.98,81.13,77.27,75.75,75.36,75.16,75.05,73.62,68.10,62.30,43.74,39.69,28.83,28.65.HRMS(ESI) calculated value C 57 H 58 N5O8[M+H] + 940.4280, measured value 940.4280.

[0539] Example 77

[0540] Preparation of compound 3-80:

[0541]

[0542] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-80 was prepared according to the following method.

[0543] 2-63 (151 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (411 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:5) to give a white solid product 3-80 (329.4 mg, 98%), which was a single β-configuration. (c1.0,CHCl3); 1H NMR(500MHz, CDCl3)δ7.30(q,J=7.3Hz,1H),7.21(d,J=8.2Hz,1H),7.17–7.07(m,3H),6.97(td,J=8 .4,2.5Hz,1H),6.87(d,J=8.3Hz,2H),6.11(bs,0.55H),5.88(bs,1H),5.78(bs,0.41H),5.72(d,J=8 .3Hz,1H),5.25(t,J=9.4Hz,1H),5.15–5.06(m,2H),5.00(s,2H),4.57–4.43(m,1H),4.41–4.32(m, 1.65H),4.25(dd,J=12.6,4.4Hz,1.50H),4.15–4.08(m,1H),3.86–3.81(m,1H),2.12–1.90(m,12H); 13 C NMR (126MHz, CDCl3): δ173.42, 172.90, 170.64, 170.09, 169.71, 169.47, 169.42, 162.95 (d, J = 246.1Hz), 157.97,154.07,139.51(d,J=7.2Hz),130.16(d,J=8.3Hz),129.88,129.41,128.87,122.74(d,J=3.0Hz), 114.96, 114.83 (d, J = 21.3 Hz), 114.21 (d, J = 22.0 Hz), 93.59, 72.67, 72.53, 72.46, 70.32, 70.20, 69.16, 69.14, 67.90, 61.41, 56.07, 55.49, 49.76, 48.99, 20.72, 20.66, 20.59, 20.56, 15.72, 14.70. HRMS (ESI) calculated value C 32 H 37 N2O 13 FNa[M+Na] + 699.2172, measured value 699.2179.

[0544] Example 78

[0545] Preparation of compound 3-81:

[0546]

[0547] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-81 was prepared according to the following method.

[0548] 2-64 (45 mg, 0.1 mmol), cesium carbonate (49 mg, 0.15 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (83 mg, 0.2 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:6) to give an orange solid product 3-81 (71.8 mg, 88%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (600MHz, CDCl3): δ8.79(d,J=13.6Hz,1H),8.36–8.15(m,1H),8.13(d,J=8.5Hz,1H),7.84–7.73(m,1H),7.53–7.30(m,2H),6.43–6 .35(m,2H),6.35–6.23(m,1H),5.74(d,J=8.4Hz,0.47H),5.72(d,J=8.3Hz,0.52H),5.29–5.21(m,1H),5.22–5.07(m,2H),4.37–4.04( m,4H),4.01–3.91(m,4H),3.91–3.79(m,1H),3.77(s,3H),3.74(s,3H),3.59–3.46(m,1H),3.44–3.30(m,1H),2.06(s,1.47H),2.03–1 .95(m,9H),1.91(s,1.47H),1.19(d,J=6.8Hz,1.86H),1.13(d,J=6.8Hz,1.44H),1.10(d,J=6.8Hz,1.75H),1.02(d,J=6.7Hz,1.58H); 13C NMR (151MHz, CDCl3): δ170.68,170.12,170.09,169.52,169.31,169.27,161.90,161.84,153.92,153.44,149.30, 148.16,147.83,139.58,138.42,138.32,137.07,136.81,130.30,129.57,129.53,123.14,122.55,103.48,103.30 ,97.25,96.53,93.28,93.14,72.96,72.81,72.49,72.43,70.37,70.16,67.99,61.59,61.51,55.50,55.44,51.91,50.91,48.89,48.24,40.22,39.87,39.43,20.99,20.78,20.69,20.67,20.64,20.61,20.58,20.49.HRMS(ESI) calculated value C 40 H 48 N6O 13 Na[M+Na] + 843.3172, measured value 843.3171.

[0549] Example 79

[0550] Preparation of compound 3-82:

[0551]

[0552] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-82 was prepared according to the following method.

[0553] 2-65 (42 mg, 0.1 mmol), potassium carbonate (21 mg, 0.15 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated twice to remove CO2, and then 1.5 mL of DMSO was added. The reaction was allowed to proceed at room temperature for 2 h. Bromoglycoside 1-2 (83 mg, 0.2 mmol) was dissolved in 1.5 mL of DMSO and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with 10 mL of water, washed with 50 mL of saturated ammonium chloride, extracted with 20 mL × 3 times of dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1–1:5) to give an orange solid product 3-82 (59.6 mg, 86%), which was in a single β configuration. (c 1.0, CHCl3); 1H NMR(600MHz, CDCl3): δ9.70(s,0.45H),9.66(s,0.43H),7.66–7.59(m,1H),7.57–7.42 (m,3H),7.33–7.23(m,2H),7.22–7.18(m,1H),5.71–5.65(m,1H),5.28–5.20(m,1H),5. 19–5.06(m,2H),4.56–4.22(m,3H),4.15–4.05(m,1H),3.84–3.78(m,1H),3.54(s,2H), 3.08(s,2H),2.89(s,1.48H),2.82(s,1.58H),2.06–1.96(m,11.23H),1.87(s,1.46H); 13 CNMR (151MHz, CDCl3): δ170.93,170.81,170.74,170.15,170.12,169.55,169.48,169.42,160.16,158.58,154.43, 153.86,136.95,136.87,136.53,136.45,135.36,135.34,131.27,131.17,128.32,128.22,127.83,124.30,123.79 ,112.28,112.23,111.61,111.43,102.04,101.87,93.53,93.40,72.78,72.65,72.52,72.43,70.30,70.15,68.01,67.93,67.89,61.61,61.50,52.59,52.12,43.15,34.80,34.03,28.75,20.75,20.64,20.62,20.55.HRMS(ESI) calculated value C 34 H 37 N3O 12 F[M+H] + 698.2356, measured value 698.2358.

[0554] Example 80

[0555] Preparation of compound 3-83:

[0556]

[0557] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-83 was prepared according to the following method.

[0558] 2-66 (150 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (411 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2.4:1) to give a white solid product 3-83 (196.0 mg, 62%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3): δ7.30–6.96(m,8H),5.83–5.69(m,1H),5.63(d,J=8.2Hz, 0.51H),5.59(d,J=8.3Hz,0.49H),5.29–5.20(m,1H),5.20–5.02(m,2H),4.37–4 .19(m,1H),4.09–3.94(m,1H),3.88–3.75(m,1H),3.53–3.11(m,4H),2.99–2.8 5(m,1H),2.85–2.66(m,4H),2.45–2.20(m,2H),2.05(s,3H),2.02–1.97(m,6H); 13 C NMR (126MHz, CDCl3): δ170.60,170.04,169.46,169.35,153.67,153.58,145.18,144.89,140.86,1 39.75,139.36,137.04,136.97,130.02,128.52,128.18,128.08,127.99,127.93,127.62,127.60, 127.25, 127.21, 126.05, 125.82, 93.14, 77.42, 77.16, 76.90, 72.74, 72.35, 72.27, 70.19, 68.02, 67.92, 61.58, 61.47, 48.94, 48.39, 33.70, 31.92, 28.01, 27.54, 20.73, 20.70, 20.58. HRMS (ESI) calculated value C 34 H 39 NO 11 Na[M+Na] + 660.2415, measured value 660.2421.

[0559] Example 81

[0560] Preparation of compound 3-84:

[0561]

[0562] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-84 was prepared according to the following method.

[0563] 2-67 (67 mg, 0.2 mmol), cesium carbonate (98 mg, 0.3 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (90 mg, 0.22 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a yellow solid product 3-84 (69.3 mg, 52%), which was a single β-configuration. (c 1.0, CHCl3); 1 HNMR (500MHz, CDCl3): δ8.35–8.28(m,1H),7.80–7.74(m,1H),7.53–7.46(m,2H),7.43–7.37(m,1H),7.33–7.24(m,1H),7.24–7.18(m,1H),7.1 4(d,J=3.5Hz,0.47H),7.07(d,J=3.6Hz,0.44H),6.96–6.90(m,1H),6.86(d,J=7.7Hz,0.49H),6.81(d,J=7.7Hz,0.45H),5.79–5.59(m,2H),5. 30–5.23(m,1H),5.22–5.09(m,2H),4.35–4.23(m,1H),4.16–4.08(m,1 H),3.87–3.82(m,1H),3.63–3.41(m,2H),2.94(s,1.49H),2.88(s,1.35 H),2.56–2.43(m,1H),2.40–2.29(m,0.50H),2.22–2.14(m,0.65H),2.1 2–2.05(m,2H),2.06–2.01(m,8.50H),1.99(s,1.30H),1.93(s,1.46H); 13C NMR (126MHz, CDCl3): δ170.76,170.18,169.58,169.47,153.83,153.74,153.12,153.04,144.53,144.48,134. 69,127.69,127.64,126.78,126.70,126.50,126.15,126.12,125.79,125.73,125.49,125.46,125.29,125.15, 125.10, 125.02, 122.06, 121.98, 120.99, 107.09, 107.05, 93.33, 74.33, 73.92, 72.85, 72.79, 72.53, 72.44, 70.29, 70.24, 68.02, 61.58, 46.70, 46.36, 37.70, 36.65, 35.68, 34.73, 20.85, 20.82, 20.70, 20.64. HRMS (ESI) calculated value C 33 H 37 NO 12 SNa[M+Na] + 694.1929, measured value 694.1937.

[0564] Example 82

[0565] Preparation of compound 3-85:

[0566]

[0567] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-85 was prepared according to the following method.

[0568] 2-68 (225 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (411 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:4-1:10) to give a yellow solid product 3-85 (376.2 mg, 91%), which was a single β-configuration. (c 1.0, CHCl3); 1H NMR (600MHz, CDCl3): δ7.72–7.67(m,1H),7.55–7.50(m,1H),7.48–7.42(m,1H),7.30–7.25 (m,1H),7.05–6.99(m,1H),6.85–6.82(m,1H),6.09–6.00(m,1H),5.65–5.59(m,1H),5.29–5 .23(m,1H),5.18–5.13(m,1H),5.13–5.07(m,1H),4.96(bs,2H),4.36–4.04(m,5H),3.88–3. 80(m,1H),3.11–2.87(m,3H),2.19–2.08(m,2H),2.09–1.91(m,14H),1.82(d,J=6.7Hz,3H); 13 C NMR (151MHz, CDCl3): δ170.69,170.10,169.53,169.46,158.43,156.77,152.64,152.53,148.96,139.96,13 6.84,136.10,136.01,134.77,130.03,128.99,128.96,123.06,122.80,122.14,122.02,120.06,119.96,118 .94,118.91,116.93,116.77,115.15,115.11,93.47,72.66,72.58,72.52,70.18,67.97,61.51,61.47,58.86,58.68,43.17,43.11,42.99,32.27,32.10,31.95,31.85,20.80,20.71,20.64,20.63,18.93.HRMS(ESI) calculated value C 36 H 41 N5O 12 Cl2FNa[M+Na] + 824.2107, measured value 824.2115.

[0569] Example 83

[0570] Preparation of compound 3-86:

[0571]

[0572] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-86 was prepared according to the following method.

[0573] 2-69 (20 mg, 0.04 mmol), cesium carbonate (20 mg, 0.06 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (33 mg, 0.08 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:4) to give a white liquid product 3-86 (31.6 mg, 90%), which was in a single β configuration. (c1.0,CHCl3); 1 H NMR (600MHz, CDCl3): δ8.34–8.27(m,2H),8.16(s,0.81H),7.34–7.28(m,1H),7.15(t,J=8.6Hz,2H),6.69(d,J=8.8Hz,0.31H),6.61(d,J= 8.6Hz,0.63H),5.63(d,J=8.3Hz,0.81H),5.60–5.48(m,1.54H),5.34–5.24(m,1.12H),5.22–5.04(m,2.08H),4.97–4.94(m,0.25H),4.74 (q,J=7.1Hz,0.62H),4.68–4.58(m,0.94H),4.55–4.47(m,0.45H),4.42(q,J=12.0Hz,0.58H),4.34–4.25(m,1.07H),4.15–4.06(m,1.31H ),3.98–3.70(m,3.39H),3.07–2.68(m,3.61H),2.46–2.39(m,1H),2.37–1.97(m,18.76H),1.84–1.57(m,10.19H),1.48–0.91(m,14.46H); 13C NMR (151MHz, CDCl3): δ222.31,185.22,172.10,172.07,171.46,171.20,171.09,170.7 4,170.64,170.55,170.15,169.81,169.73,169.57,169.55,166.64,164.95,154.58,1 53.98, 153.55, 153.36, 139.21, 133.51, 133.45, 128.48, 128.42, 128.35, 127.37, 127.24, 115.49, 115.35, 113.37, 93.81, 74.23, 72.71, 72.66, 72.60, 72.41, 70.34, 69.93, 68 .18,67.97,61.68,61.54,58.82,55.32,55.23,54.91,54.70,50.93,47.73,47.67,42.32,41.49,41.04,40.93,38.99,35.72,33.35,32.07,31.67,30.53,30.46,30.16,30.0 7,28.35,28.13,27.43,26.17,26.02,26.00,25.88,25.59,24.69,22.25,21.43,21.29,20.85,20.79,20.71,20.69,20.63,20.20,18.39,14.65,14.31,13.95.HRMS(ESI) calculated value C 41 H 51 N4O 14 SFNa[M+Na] + 897.2999, measured value 897.3001.

[0574] Example 84

[0575] Preparation of compound 3-87:

[0576]

[0577] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-87 was prepared according to the following method.

[0578] 2-70 (19 mg, 0.05 mmol), cesium carbonate (25 mg, 0.075 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (41 mg, 0.1 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:4) to give a white solid product 3-87 (27.7 mg, 73%), which was a single β-configuration. (c 1.0, CHCl3); 1 H NMR (600MHz, CDCl3): δ11.61(bs,1H),7.27(s,1H),6.57(s,1H),5.65–5.59 (m,1H),5.30–5.23(m,1H),5.18–5.08(m,2H),4.34–4.27(m,1H),4.21–4.1 5(m,1H),4.13–4.04(m,1H),3.95(s,2H),3.87–3.81(m,1H),3.03–2.88(m, 2H),2.62–2.53(m,1H),2.11–1.99(m,12H),1.94–1.75(m,4H),1.23(s,9H); 13 CNMR (151MHz, CDCl3): δ172.30,172.24,170.85,170.76,170.18,170.16,169.59,169.57,16 9.50,162.63,162.00,158.89,152.70,152.55,143.55,121.64,120.22,93.48,72.75,72.61, 72.57, 70.23, 70.19, 68.05, 68.01, 61.59, 61.55, 43.43, 43.37, 43.33, 43.26, 42.30, 42.16, 34.94, 31.55, 28.66, 28.10, 27.89, 20.88, 20.86, 20.78, 20.76, 20.70, 20.69. HRMS (ESI) calculated value C 32 H 42 N4O 13 S2Na[M+Na] + 777.2082, measured value 777.2077.

[0579] Example 85

[0580] Preparation of compound 3-88:

[0581]

[0582] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-88 was prepared according to the following method.

[0583] 2-71 (171 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill the system with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (411 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2.4:4) to give a white solid product 3-88 (355.4 mg, >99%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3): δ7.32(d,J=8.3Hz,1H),7.31–7.16(m,2.83H),7.10–7.02(m,1.57H),6.98–6.93(m,1H),6.81–6.7 6(m,1H),5.79(d,J=8.2Hz,0.56H),5.71(d,J=8.3Hz,0.43H),5.45(dt,J=10.3,5.8Hz,0.58H),5.39–5.20(m,2H),5.20 –5.09(m,1.45H),4.36–4.29(m,1H),4.24–4.07(m,2H),3.91–3.85(m,1H),2.70(s,1.26H),2.66(s,1.68H),2.35–2.23 (m,1H),2.11(s,1.75H),2.08(s,3.13H),2.08–1.95(m,9.52H),1.82–1.66(m,2.41H),1.55(dq,J=11.3,3.2Hz,0.50H); 13C NMR (126MHz, CDCl3): δ170.80,170.77,170.21,170.19,169.58,169.44,169.33,154.85,154.5 0,146.95,146.90,138.46,138.05,135.65,135.37,132.50,131.11,130.94,130.72,130.35,13 0.27, 128.09, 127.81, 127.68, 127.51, 126.86, 93.65, 93.56, 72.73, 72.55, 70.57, 70.27, 68.10, 68.01, 61.58, 55.56, 43.09, 30.05, 29.97, 22.60, 21.74, 20.87, 20.74, 20.71. HRMS (ESI) calculated value C 32 H 35 NO 11 Cl2Na[M+Na] + 702.1479, measured value 702.1482.

[0584] Example 86

[0585] Preparation of compound 3-89:

[0586]

[0587] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compounds 3-89 were prepared according to the following method.

[0588] 2-72 (23 mg, 0.05 mmol), cesium carbonate (25 mg, 0.075 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (41 mg, 0.1 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:3) to give a yellow solid product 3-89 (40.6 mg, 97%), which was a single β-configuration. (c 0.4, CHCl3); 1H NMR (600MHz, CDCl3): δ8.64(s,1H),8.18–8.12(m,2H),7.99–7.94(m,2H),7.90–7.82(m,2H),7.39–7.34(m,2H),7.33 –7.27(m,1H),6.14(bs,2H),5.72(d,J=8.3Hz,1H),5.32–5.23(m,1H),5.24–5.10(m,2H),4.66–4.59(m,0.48H),4.56 –4.48(m,1H),4.42–4.26(m,1.52H),4.20–4.06(m,1.53H),3.90–3.84(m,1H),3.28–3.19(m,1H),2.94(s,1.52H),2. 86(s,1.52H),2.09–2.05(m,3H),2.04–1.99(m,6H),1.99–1.96(m,1.67H),1.92–1.87(m,1.96H),1.35–1.27(m,6H); 13 C NMR (151MHz, CDCl3): δ170.74,170.17,169.57,169.47,169.44,169.36,162.51,162.47,154.44,153.86,150 .89,150.86,141.28,140.04,139.99,139.39,139.31,136.63,136.59,129.85,128.60,128.03,127.85,127. 74,127.44,126.11,125.93,102.20,102.17,102.14,93.58,93.49,72.86,72.73,72.64,72.54,70.36,70.13,68.03,61.58,55.81,52.72,52.25,34.88,34.09,20.85,20.72,20.68,20.66,20.60,15.84.HRMS(ESI) calculated value C 39 H 43 N5O 14 SNa[M+Na] + 860.2419, measured value 860.2423.

[0589] Example 87

[0590] Preparation of compound 3-90:

[0591]

[0592] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-90 was prepared according to the following method.

[0593] 2-73 (81 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (411 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:2) to give a white solid product 3-90 (267.2 mg, 50%), which was a single β-configuration. (c 1.0,CH2Cl2); 1 HNMR(500MHz, CDCl3)δ8.53–8.36(m,2H),7.64–7.40(m,1H),7.30–7.20(m,1 H),5.69(d,J=8.3Hz,1H),5.55–5.33(m,1H),5.25(t,J=9.5Hz,1H),5.20–4.9 9(m,2H),4.34–4.18(m,1H),4.14–3.95(m,2H),3.82(d,J=10.1Hz,1H),2.72 (t,J=13.2Hz,1H),2.37–2.23(m,1H),2.08–1.94(m,13H),1.71–1.36(m,4H); 13 C NMR (126MHz, CDCl3) δ 170.65, 170.07, 169.47, 169.43, 153.58, 148.34, 148.27, 134.56, 123.54, 93.58, 72.62, 72.53, 70.32, 67.99, 61.49, 52.24, 40.71, 27.52, 25.15, 20.78, 20.67, 20.63, 20.61, 19.08. HRMS (ESI) calculated C 25 H 33 N2O 11 Na[M+Na] + 537.2079, measured value 537.2081.

[0594] Example 88

[0595] Preparation of compound 3-91:

[0596]

[0597] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-91 was prepared according to the following method.

[0598] 2-74 (86 mg, 0.25 mmol), cesium carbonate (122 mg, 0.375 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (206 mg, 0.5 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:4) to give a yellow solid product 3-91 (187.3 mg, >99%), which was a single β-configuration. (c1.0,CHCl3); 1 H NMR (500MHz, CDCl3): δ8.77–8.72(m,1H),8.59–8.53(m,1H),7.69–7.63(m,1H),7.44–7.29(m,3H),7.1 6–7.08(m,2H),7.03–6.96(m,1H),6.20(d,J=1.9Hz,0.45H),6.15(d,J=1.9Hz,0.49H),5.68(d,J=8.3H z,0.52H),5.65(d,J=8.3Hz,0.48H),5.28–5.21(m,1H),5.20–5.14(m,1H),5.14–5.05(m,1H),4.33–4. 16(m,3H),4.13–4.02(m,1H),3.86–3.78(m,1H),2.87(s,1.52H),2.82(s,1.44H),2.08–1.94(m,12H); 13C NMR (126MHz, CDCl3): δ170.69,170.12,169.54,169.53,169.44,160.69(d,J=249.4Hz),154.37,154.03,153.51,1 47.97,135.01,134.74,133.26,131.46,131.40,129.35,129.32,123.86,123.76,123.58,123.50(d,J=3.7Hz),12 2.01, 121.88, 118.78, 118.62, 117.78, 117.58, 115.45 (d, J = 21.8 Hz), 93.45, 93.42, 72.82, 72.68, 72.57, 72.48, 70.29, 70.12, 67.96, 61.52, 45.43, 45.04, 34.36, 33.80, 20.77, 20.69, 20.66, 20.65, 20.60, 20.53. HRMS (ESI) calculated value C 32 H 34 N3O 13 SFNa[M+Na] + 742.1689, measured value 742.1699.

[0599] Example 89

[0600] Preparation of compound 3-92:

[0601]

[0602] Chlorinated glycoside 1-1 was prepared according to the literature (Carbohydrate Research. 2008, 343, 2989-2991), and then compound 3-92 was prepared by the following steps:

[0603] 2-75 (170 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Chlorinated glycoside 1-1 (366 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:3) to give a white solid product 3-91 (187.3 mg, 96%), which was a single β-configuration. (c1.0,CHCl3); 1H NMR (500MHz, CDCl3) δ7.67(d,J=7.8Hz,1H),7.56–7.47(m,1H),7.35(t,J=7.6Hz,1H),7.11(d,J=7.9Hz,1H),5.56(d,J =8.4Hz,1H),5.35–5.14(m,5H),5.06(t,J=9.7Hz,1H),5.00(t,J=9.0Hz,1H),4.27(dd,J=12.5,4.2Hz,1H),4.12–4.00 (m,1H),3.78(ddd,J=10.1,4.2,2.3Hz,1H),3.74–3.65(m,1H),3.24(s,3H),3.21–3.15(m,1H),2.91–2.42(m,3H),2.0 3(s,3H),2.00–1.97(m,6H),1.95(s,3H),1.91–1.80(m,1H),1.80–1.72(m,1H),1.66–1.56(m,1H),1.48–1.37(m,1H); 13 C NMR (126MHz, CDCl3) δ 170.54, 169.99, 169.50, 169.49, 162.96, 159.32, 152.85, 152.54, 140.46, 133.41, 133.31, 128.11, 126.95, 117.17, 110.74, 92.71, 90.86, 72.79, 72.38, 70.13, 67.74, 61.43, 55.42, 46.06, 28.00, 20.72, 20.62, 20.55. HRMS (ESI) calculated C 33 H 39 N5O 13 Na[M+Na] + 736.2437, measured value 736.2438.

[0604] Example 90

[0605] Preparation of compound 3-93:

[0606]

[0607] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-93 was prepared according to the following method.

[0608] 2-76 (146 mg, 0.5 mmol), cesium carbonate (245 mg, 0.75 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (411 mg, 1.0 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 2:1) to give a white solid product 3-93 (270.9 mg, 86%), which was a single β-configuration. (c 1.0, CHCl3); 1 H NMR (500MHz, CDCl3): δ7.36–7.27(m,4H),7.25–7.20(m,1H),7.13–7.07(m,1H),6.98–6.89(m,1H),6.82–6 .72(m,1H),6.59(d,J=8.7Hz,0.53H),6.55(d,J=8.2Hz,0.46H),5.61(d,J=8.4Hz,1H),5.28–5.05(m,3H),4 .99(dd,J=9.6,8.4Hz,0.52H),4.34–4.23(m,1H),4.13–4.06(m,1H),3.85–3.77(m,1H),3.58–3.35(m,2H) ,2.90(s,1.59H),2.84(s,1.44H),2.34(s,1.57H),2.32(s,1.46H),2.26–2.08(m,2H),2.04–1.97(m,12H); 13C NMR (126MHz, CDCl3): δ170.68,170.14,170.11,169.52,169.37,169.17,155.72,155.64,153.80,153.66,141. 54,141.47,130.73,130.71,128.76,127.74,126.99,126.97,126.64,125.73,125.67,120.48,120.45,112.71, 112.67,93.25,93.23,77.33,77.29,76.72,72.88,72.75,72.46,72.32,70.23,70.14,69.88,67.98,61.63,61.53,46.81,46.18,37.59,36.56,35.52,34.64,20.79,20.76,20.66,20.64,20.54,16.60,16.58. HRMS(ESI) calculated value C 32 H 39 NO 12 Na[M+Na] + 652.2364, measured value 652.2365.

[0609] Example 91

[0610] Preparation of compound 3-94:

[0611]

[0612] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-94 was prepared according to the following method.

[0613] 2-77 (9 mg, 0.0176 mmol), cesium carbonate (9 mg, 0.0264 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was carried out at room temperature for 2 h. Bromoglycoside 1-2 (15 mg, 0.0352 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1 - DCM:MeOH = 3:1) to give a white solid product 3-94 (12 mg, 77%), which was a single β-configuration. (c 1.0, CHCl3); 1H NMR (600MHz, CDCl3): δ8.32(s,0.46H),8.28(s,0.48H),7.36–7.30(m,1H),7.04–7.00(m,1 H),6.55(bs,1H),6.45(bs,1H),6.01(s,2H),5.67–5.62(m,1H),5.27–5.22(m,1H),5.21–5 .05(m,2H),4.34–4.18(m,3H),4.19–4.07(m,2H),3.85–3.79(m,1H),3.31–3.16(m,2H),3. 10–3.01(m,0.78H),2.17–2.08(m,1H),2.08–1.99(m,12H),1.97(s,2H),1.19–1.02(m,6H). 13 C NMR (151MHz, CDCl3): δ170.75,170.22,169.68,169.59,169.42,169.38,153.70,153.14,152.96,151.48, 149.91,149.66,149.48,148.39,126.64,126.50,119.93,119.58,113.53,113.45,102.60,93.27,93.20,9 3.14, 93.03, 72.90, 72.84, 72.57, 70.48, 70.24, 68.20, 68.06, 61.77, 61.59, 48.72, 48.21, 42.14, 42.02, 40.79, 40.39, 30.58, 29.94, 29.83, 29.79, 21.15, 20.93, 20.90, 20.78, 20.73, 20.48, 20.45. HRMS (ESI) calculated value C 33 H 39 N6O 13 SINa[M+Na] + 909.1233, measured value 909.1226.

[0614] Example 92

[0615] Preparation of compound 3-95:

[0616]

[0617] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-95 was prepared according to the following method.

[0618] Place 2-78 (21 mg, 0.05 mmol), cesium carbonate (25 mg, 0.075 mmol), and a stir bar into a 25 mL Schlenk tube. In the process, the system was evacuated and CO2 was replaced twice to fill it with CO2. Then, 1.5 mL of DMSO was added, and the reaction was carried out at room temperature for 2 hours. Bromoglycosides 1-2 (41 The product (mg, 0.1 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1-1:4) to give a white solid product 3-95 (38.9 mg, 98%). The product was a single β configuration. (c1.0,CHCl3); 1 H NMR (600MHz, CDCl3): δ7.52–7.47(m,2H),7.34–7.31(d,J=7.9Hz,0.74H),7.31–7.28(d,J=7.8Hz,1.38H),7.26–7.23(m,1H),7.21–7. 17(m,1.33H),7.14(d,J=8.9Hz,0.33H),7.09–7.07(m,1H),7.05(d,J=9.1Hz,0.65H),5.63(d,J=8.1Hz,0.35H),5.59(d,J=8.3Hz,0.6 5H),5.25–5.17(m,1H),5.16–5.03(m,3H),4.21–4.13(m,1H),4.12–3.97(m,4H),3.78–3.72(m,1H),3.67(dt,J=14.2,5.9Hz,0.32H), 3.55–3.41(m,2.35H),3.41–3.28(m,4.23H),3.19–2.99(m,2.34H),2.05–1.93(m,12H),1.91–1.86(m,1.33H),1.79–1.70(m,0.70H). 13C NMR (151MHz, CDCl3): δ170.74,170.56,170.16,170.05,169.53,169.46,169.43,169.12,168.84,154.96,153.37,142. 38,140.38,140.35,137.16,137.13,133.33,133.19,132.42,130.26,130.15,127.79,121.60,117.90,110.19,106.95 ,93.50,93.47,79.56,78.70,72.62,72.58,72.52,70.47,70.29,69.85,69.10,67.97,67.87,61.42,61.34,51.32,50.86,46.44,45.82,41.41,41.09,38.86,38.69,30.08,29.19,28.30,20.81,20.77,20.71,20.68,20.65.HRMS(ESI) calculated value C 38 H 42 N4O 15 Na[M+Na] + 817.2539, measured value 817.2546.

[0619] Example 93

[0620] Preparation of compound 3-96:

[0621]

[0622] Bromoglycosides 1-2 were purchased from Shanghai Titan Technology Co., Ltd. (adamas), and compound 3-96 was prepared according to the following method.

[0623] 2-79 (145 mg, 0.25 mmol), cesium carbonate (122 mg, 0.375 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (1.5 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Bromoglycoside 1-2 (206 mg, 0.5 mmol) was dissolved in DMSO (1.5 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1–1:8) to give a white solid product 3-96 (230.4 mg, 97%), which was in a single β configuration. (c0.1,CH2Cl2); 1H NMR(500MHz,CDCl3):δ8.64(s,2H),8.39(s,1H),7.92–7.86(m,2H),7.85–7.79(m,1H),7.71–7.63(m,1H),7.37–7.29(m,1H),7.24–7.14(m,2H),7.02–6.96(m,1H),6.96–6.91(m,1H),6.73–6.68(m,1H),6.47–6.41(m,1H),5.66(d,J=7.6Hz,0.44H),5.63(d,J=8.2Hz,0.55H),5.33–5.24(m,1.46H),5.20–5.07(m,3.56H),4.74(d,J=16.0Hz,0.43H),4.65(d,J=15.7Hz,0.55H),4.58(d,J=15.8Hz,0.55H),4.38(d,J=16.0Hz,0.43H),4.34–4.25(m,1H),4.17–4.02(m,2.81H),4.02–3.88(m,1H),3.87–3.81(m,1H),3.54–3.44(m,0.45H),3.44–3.27(m,1.55H),3.00(s,1.66H),2.92(s,1.33H),2.10–1.96(m,12H). 13 C NMR(126MHz,CDCl3):δ170.62,170.08,169.94,169.83,169.52,163.03(d,J=246.3Hz),158.01,153.46,153.32,153.12,152.88,150.88,150.20,150.10,139.26,139.20,132.66,130.24(d,J=8.1Hz),129.08,128.20,125.00,124.94,123.12,123.08,122.51,122.28,122.20,115.60,114.93(d,J=21.2Hz),114.17,114.02(d,J=21.8Hz),112.27,112.04,107.63,93.70,93.61,72.61,72.54,72.25,70.36,70.29,70.11,67.80,61.41,61.28,52.61,52.18,44.59,44.50,41.46,41.17,20.81,20.79,20.62,20.59. 19FNMR (376MHz, CDCl3) δ -112.60, -112.62. HRMS (ESI) calculated value C 44 H 45 ClFN4O 15 S[M+H] + 955.2286, measured value 955.2269.

[0624] Comparative Example 1

[0625]

[0626] 2-42 (160 μL, 1.0 mmol), cesium carbonate (490 mg, 1.5 mmol), and a stir bar were placed in a 25 mL Schlenk tube. The tube was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (3 mL) was added, and the reaction was allowed to proceed at room temperature for 2 h. Bromoglycoside E1 (1.27 g, 3.0 mmol) was dissolved in DMSO (3 mL) and added to the system. The reaction was allowed to proceed at room temperature for 12 h. The reaction mixture was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (toluene:EA = 10:1) to give product 3-97 (yield 31.6%). NMR analysis showed that the product was a mixture of α:β = 1:1. 1H NMR(600MHz,CDCl3)δ8.12(d,J=8.5Hz,0.50H),8.09–8.03(m,1.90H),8.00(d,J=8.4Hz,0.73H),7.93(dt,J=8.3,1.5Hz,1.84H),7.88(d,J=8.1Hz,0.56H),7.87–7.83(m,0.50H),7.82(d,J=8.1Hz,0.56H),7.77(d,J=8.2Hz,0.55H),7.66–7.59(m,0.55H),7.59–7.53(m,1.58H),7.53–7.38(m,5.43H),7.33(ddd,J=18.3,10.7,7.3Hz,1.97H),7.19(t,J=7.8Hz,0.98H),6.47(d,J=10.1Hz,0.47H),6.46(d,J=4.6Hz,0.50H),5.88(dt,J=16.9,5.9Hz,0.44H),5.71(p,J=7.0Hz,0.46H),5.56(p,J=7.0Hz,0.47H),5.50(dd,J=21.3,4.0Hz,0.53H),5.44(dd,J=6.2,4.5Hz,0.55H),5.36(dd,J=6.2,4.6Hz,0.59H),5.21(d,J=48.6Hz,0.59H),5.07(d,J=8.1Hz,0.56H),4.87(d,J=8.0Hz,0.46H),4.78(dd,J=12.0,3.7Hz,0.47),4.72(dd,J=11.6,3.5Hz,0.49H),4.69–4.63(m,0.95H),4.48(dd,J=12.0,5.2Hz,0.51H),4.41(td,J=5.4,3.7Hz,0.50H),1.72(d,J=6.8Hz,1.44H),1.57(d,J=6.8Hz,1.40H).13C NMR(151MHz,CDCl3)δ166.38,165.90,165.62,153.36,153.22,138.11,137.98,134.14,134.08,133.98,133.86,133.32,133.20,131.03,130.92,130.04,129.99,129.93,129.75,129.69,129.08,128.95,128.83,128.76,128.73,128.69,128.53,128.48,128.42,126.84,126.65,126.13,125.96, 125.38, 123.25, 123.15, 122.58, 122.42, 100.10 (d, J = 37.6 Hz), 97.81 (d, J = 184.5 Hz), 93.90 (d, J = 16.9 Hz), 92.64 (d, J = 202.5 Hz), 83.35, 79.90 (d, J = 7.2 Hz), 77.37, 77.16, 76.95, 75.62 (d, J = 24.8 Hz), 64.35, 63.64, 46.90, 46.87, 21.45, 21.39. ESI-MS: 580.3 (M + Na) HRMS (ESI) calculated value C. 32 H 28 FNO7Na[M+Na]+580.1748, measured value 547.1742.

[0627] Comparative Example 2

[0628]

[0629] 2-41 (57 mg, 0.3 mmol), cesium carbonate (147 mg, 0.45 mmol), and a stir bar were placed in a 25 mL Shrek reaction tube. The system was evacuated and CO2 was replaced twice to fill it with CO2. DMSO (2 mL) was added, and the reaction was carried out at room temperature for 2 h. Chloroglucinol 2-β (220 mg, 0.6 mmol) was dissolved in DMSO (2 mL) and added to the system. The reaction was carried out at room temperature for 12 h. The reaction solution was quenched with water (10 mL), washed with saturated ammonium chloride (50 mL), extracted with dichloromethane (20 mL × 3), dried over anhydrous sodium sulfate, filtered, concentrated, and subjected to column chromatography (PE:EA = 1:1–1:3) to obtain a white solid product 3-98 (27.2 mg, 16%). NMR analysis showed that the product was a mixture of α and β molecules in a ratio of α / β = 1 / 0.6. The characterization data of the product are as follows: 1 ¹H NMR (500MHz, CDCl₃) δ 7.59–7.33 (m, 8.1H), 6.27 (d, J = 3.7Hz, 1.0H, H₁-α), 5.61 (d, J = 8.3Hz, 0.6H, H₁-β), 5.38 (bs, 1.15H), 5.32–5.19 (m, 1.16H), 5.19–5.06 (m, 3.32H), 4.40–4.19 (m, 2.29H), 4.15–3.97 (m, 3.88H), 3.94–3.19 (m, 14.85H), 2.07 (s, 4.8H), 2.04–1.97 (m, 14.4H). HRMS (ESI) calculated C 26 H 32 N2O 12 Na[M+Na]+ 587.1847, measured value 587.1853.

[0630] Example 1

[0631] Cell viability assay procedure:

[0632] HEK-293T cells, SK-MEL-28 cells, and SNU-5 cells were provided by the Cell Bank of the Chinese Academy of Sciences.

[0633] Cells (HEK-293T cells, SK-MEL-28 cells, and SNU-5 cells) were viable at 3 × 10⁻⁶. 3 Cells were seeded at a density of 1 / 2 well to 96 cells and cultured in 100 μL of medium. After 24 hours of culture, cells were treated with different concentrations of the compound (0, 5 nM, 30 μM, 50 nM, 300 nM, 500 nM, 3 μM, 5 μM, 30 μM, 50 μM). After 72 hours of treatment, 10 μL of CCK-8 reagent was added to each well, and the cells were cultured for 4 hours. All experiments were performed in triplicate, with cell-free wells used as blank controls. Absorbance was measured at 450 nm using a microplate reader. Cell proliferation was expressed by absorbance, and data were processed using Prism (GraphPad).

[0634] The synthetic steps and characterization data of compound 4-1 are as follows:

[0635]

[0636] Dissolve 3-85 (20 mg, 0.024 mmol) and potassium carbonate (1.7 mg, 0.012 mmol) in 1 mL of methanol and react at room temperature for 30 min. Monitor the reaction by TLC until complete. Add acidic resin to adjust the pH to neutral. The system is clear. Filter with diatomaceous earth and concentrate to obtain yellow syrup 4-1 (0.0129 g, 81%). (c 1.0, CH3OH); 1H NMR(500MHz,Methanol-d4)δ7.82(d,J=0.8Hz,1H),7.67(s,1H),7.55(d,J=0.8Hz,1H) ,7.45(dd,J=9.0,4.7Hz,1H),7.29–7.18(m,1H),6.93(d,J=1.8Hz,1H),6.17(q,J=6.7H z,1H),5.38(d,J=8.0Hz,1H),4.46–4.24(m,3H),3.84(m,2H),3.73-3.66(m,1H),3.38- 3.34(m,2H),3.15–2.94(m,2H),2.15-2.05(m,2H),1.93(s,2H),1.87(d,J=6.6Hz,3H).

[0637] HRMS (ESI) calculated value: [C 28 H 33 [N5O8Cl2F]Na + 678.1504. Measured value: 678.1510.

[0638] The experimental data results are shown in Table 1:

[0639] Table 1

[0640]

[0641] The experimental results show that the two glycosylation modification products of Crizotinib—peracetylglucosylation modification product 3-85 and glucosylation modification product 4-1—exhibit good inhibitory activity against tumor cells HEK-293T, SK-MEL-28, and SNU-5. The inhibitory activity of peracetylglucosylation modification product 3-85 against tumor cells HEK-293T and SK-MEL-28 is comparable to that of Crizotinib and superior to that of glucosylation modification product 4-1. The inhibitory activity of peracetylglucosylation modification products 3-85 and glucosylation modification product 4-1 against tumor cells SNU-5 is comparable to that of Crizotinib. This indicates that the two glycosylation modification products can release the original drug through intracellular degradation. The glycosylation modification strategy adopted by this method can indeed play the role of a prodrug, and the inhibitory activity of peracetylglucosylation modification product 3-85 against tumor cells HEK-293T and SK-MEL-28 is superior to that of glucosylation modification product 4-1.

Claims

1. A method for preparing a 1-O-glycosylcarbamate compound, characterized in that, It includes the following steps: (1) In a solvent, under alkaline conditions, amine compounds are subjected to carbamate reaction with carbon dioxide; (2) After the reaction in step (1) is completed, the glycosylation reaction is carried out with the halogenated glycoside to obtain the corresponding 1-O-glycosyl carbamate compound; The amine compounds are compounds containing primary or secondary amine groups, wherein the N atom in the primary or secondary amine group is bonded to at least one sp3 hybridized C atom, and is not directly bonded to carbonyl, O, N, S, P heteroatoms or heteroaryl groups. The halogenated glycosides are glycosides containing a carbon-halogen bond at the 1-position of the sugar ring, including: substituted α-D-glucopyranoside, substituted 2-fluoro-2-deoxy-α-D-glucopyranoside, substituted 6-fluoro-6-deoxy-α-D-glucopyranoside, substituted α-D-galactopyranoside, substituted α-D-glucopyranoside, substituted β-D / L-arabinopyranoside, and substituted α- D / L-pyranoxyloside, substituted α-D / L-pyranoxyloside, or substituted α-D / L-pyranoxyloside; wherein when the halogen in the halogen is chlorine, the substituents are each independently selected from acetyl, benzoyl, benzyl, methoxy-substituted benzyl, allyl, or fully substituted 1-glycosyl; wherein when the halogen in the halogen is bromine or iodine, the substituents are each independently selected from acetyl, benzoyl, or fully substituted 1-glycosyl.

2. The method for preparing the 1-O-glycosylcarbamate compound according to claim 1, characterized in that, The preparation method described herein satisfies one or more of the following conditions: 1) The solvent is one or more of the following: sulfur-containing compound solvents, nitrogen-containing compound solvents, hydrocarbon solvents, haloalkane solvents, ketone solvents, or ester solvents; 2) The alkali is one or more of inorganic alkali and organic alkali; 3) In the amine compounds described above, the number of primary or secondary amine groups is one or more; 4) The molar volume ratio of the amine compound to the solvent is 0.01 mol / L to 10.0 mol / L; 5) The molar ratio of the amine compound to the base, based on the number of primary or secondary amine groups it contains, is 1:1 to 1:

5. 6) CO2 can be added via a bubbling method; 7) The partial pressure of CO2 is between 0.01 and 2 MPa; 8) The temperature of the carbamate reaction is 10-40℃; 9) The halogenated glycoside is a substituted α-D-glucopyranoside, a substituted 2-fluoro-2-deoxy-α-D-glucopyranoside, a substituted 6-fluoro-6-deoxy-α-D-glucopyranoside, a substituted α-D-galactopyranoside, a substituted β-D / L-arabinopyranoside, a substituted α-D / L-xylopyranoside, a substituted α-D / L-fucoside, or a substituted α-D / L-cellobiose glycoside, wherein when the halogen in the halogenated glycoside is chlorine, each substituent is independently selected from acetyl, benzyl, or a fully substituted 1-glycosyl group; when the halogen in the halogenated glycoside is bromine or iodine, the substituent is acetyl. 10) When the halogenated glycoside is in the α configuration, the glycosidic bond of the corresponding 1-O-glycosylcarbamate compound is in the β configuration; 11) When the halogenated glycoside is in the β configuration, the glycosidic bond of the corresponding 1-O-glycosylcarbamate compound is in the α configuration; 12) Each of the fully substituted 1-glycosyl groups is independently selected from fully substituted β-D-glucosyl, fully substituted α-D-glucosyl, fully substituted β-D-galactosyl, fully substituted α-D-galactosyl, fully substituted β-D-mannosyl, fully substituted α-D-mannosyl, fully substituted β-D-xylose, fully substituted α-D-xylose, fully substituted β-D-2-aminoglucosyl, and fully substituted α-D-2-aminoglucosyl. Glucosyl, fully substituted α-L-rhamnosyl, fully substituted β-L-rhamnosyl, fully substituted α-D-ribosyl, fully substituted β-D-ribosyl, fully substituted α-L-ribosyl, fully substituted β-L-ribosyl, fully substituted α-D-arabinose, fully substituted β-D-arabinose, fully substituted α-L-arabinose, fully substituted β-L-arabinose, fully substituted α-L-fucosyl, fully substituted β-L-fucosylation, fully substituted β-D-glucuronic acid, fully substituted α-D-glucuronic acid, fully substituted β-D-galacturonic acid, fully substituted α-D-galacturonic acid, fully substituted β-2-deoxy-D-glucosyl, fully substituted α-2-deoxy-D-glucosyl, fully substituted β-2-deoxy-D-galactosyl, fully substituted α-2-deoxy-D-galactosyl, fully substituted α-2-deoxy- -D-ribosyl, fully substituted β-2-deoxy-D-ribosyl, fully substituted α-2-deoxy-L-ribosyl, fully substituted β-2-deoxy-L-ribosyl, fully substituted β-2-(acetylamino)-2-deoxy-D-glucosyl, fully substituted α-2-(acetylamino)-2-deoxy-D-glucosyl; wherein the fully substituted groups on the glycosyl group are each independently selected from acetyl, benzoyl, benzyl or p-methoxybenzyl; 13) The molar ratio of the amine compound to the haloglycoside, based on the number of primary or secondary amine groups it contains, is 1:1 to 1:

5. 14) The molar volume ratio of the haloglycoside to the solvent is 0.01 mol / L to 10 mol / L; and 15) After the glycosylation reaction is completed, post-processing steps are also included: quenching, washing, organic solvent extraction, and concentration; for example, quenching the reaction solution with water, washing with saturated ammonium chloride, extracting with dichloromethane, drying with anhydrous sodium sulfate, filtering, and concentrating.

3. The method for preparing the 1-O-glycosylcarbamate compound according to claim 2, characterized in that, The preparation method described herein satisfies one or more of the following conditions: 1) The sulfur-containing compound solvent is dimethyl sulfoxide, the nitrogen-containing compound solvent is one or more of N,N-dimethylformamide, N-methylpyrrolidone and acetonitrile, the hydrocarbon solvent is one or more of benzene, toluene and xylene, the haloalkane solvent is one or more of dichloromethane, trichloromethane, 1,2-dichloroethane, trifluorotoluene, chlorobenzene and fluorobenzene, the ketone solvent is acetone, and the ester solvent is ethyl acetate. Preferably, the solvent is dimethyl sulfoxide and / or N,N-dimethylformamide. 2) The inorganic base in the base is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate and potassium phosphate, and the organic base is one or more of triethylamine, N,N-diisopropylethylamine, dimethylaminopyridine and 1,8-diazabicycloundec-7-ene. Preferably, the base is cesium carbonate and / or potassium carbonate. 3) In the amine compounds described above, the number of primary or secondary amine groups is 1, 2, 3, 4, or 5; 4) In the amine compounds described above, the group attached to the primary or secondary amine is selected from groups formed by one or more substituents connected together, namely: alkyl, alkenyl, alkynyl, cyano, heteroalkyl, cycloalkyl, heterocycloalkyl, heterocycloalkenyl, aryl, and heteroaryl; when the group is formed by multiple substituents connected together, the substituents may be the same or different; the substituents may optionally be connected by one or more R... 1 Replace; R 1 Independent of halogen, halogenated C 1-10 Alkyl, -OH, -CN, -SH, -NO2, -C(=O)-NH2, -S(=O)-NH2 or =O; "heterogeneous" represents N, O, S, -C(=O)-, -C(=S)-, -S(=O)-, -S(=O)2-, -C(=O)O-, The number of heteroatoms or heterogroups is selected from 1, 2, 3, 4, 5 or 6; 5) The molar volume ratio of the amine compound to the solvent is 0.01 mol / L to 4 mol / L; 6) The molar ratio of the amine compound to the base is 1:1.5; 7) The partial pressure of CO2 is 0.1 MPa; 8) The temperature of the carbamate reaction is room temperature; 9) The molar ratio of the amine compound to the haloglycoside is 1:1 to 1:3; and 10) The molar volume ratio of the haloglycoside to the solvent is 0.01 mol / L to 4 mol / L; Preferably, the amine compound satisfies one or more of the following conditions: 1) The alkyl group in the group is independently C 1-20 Alkyl group, preferably C 1-10 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; 2) The alkenyl group is independently C 2-6 Alkenyl group, preferably C 2-4 alkenyl, for example 3) The alkynyl group is independently C 2-6 Alkyne group, preferably C 2-4 Alkyne groups, such as ethynyl groups; 4) The cyano group is independently C 2-6 Cyano group, preferably C 2-4 Cyano, for example 5) The heteroalkyl group is independently C 1-19 Heteroalkyl, preferably C 2-9 Heteroalkyl groups, wherein one, two, three, or four heteroatoms or heterogroups are selected from N, O, S, S(=O), or S(=O)2; for example 6) The cycloalkyl group is independently C 3-20 Cycloalkyl, preferably C 3-10 cycloalkyl; for example 7) The heterocyclic alkyl group is independently C 3-20 Heterocyclic alkyl groups, preferably C 5-9 Heterocyclic alkyl groups, containing 1, 2, 3, or 4 heteroatoms or heterogroups selected from N, O, S, S(=O), or S(=O)2; for example, piperidinyl, 8) The heterocyclic alkenyl group is independently C 3-19 Heterocyclic alkenyl groups, preferably C 5-9 Heterocyclic alkenyl groups, containing 1, 2, 3, or 4 heteroatoms or heterogroups selected from N, O, S, S(=O), or S(=O)2; for example 9) The aryl group is independently C 6-20 Aryl, preferably C 6-14 Aryl groups, such as phenyl, benzyl, naphthyl, or biphenyl; and 10) The heteroaryl group is independently C 5-19 heteroaryl, preferably C 5-9 Heteroaryl groups, which contain 1, 2, 3 or 4 heteroatoms or heteroatomic groups selected from N, O, S, S(=O), or S(=O)2; for example, pyrrole, thiophene, furanyl, pyridyl, indolyl or imidazolyl.

4. The method for preparing the 1-O-glycosylcarbamate compound according to claim 3, characterized in that, The primary amine compounds mentioned above are any of the following compounds: And / or, the secondary amine compounds in the amine compounds are any of the following compounds:

5. The method for preparing the 1-O-glycosylcarbamate compound according to claim 3, characterized in that, The haloglycoside is any of the following compounds:

6. The method for preparing the 1-O-glycosylcarbamate compound according to any one of claims 1-5, characterized in that, The 1-O-glycosylcarbamate compound is any one of the following compounds:

7. The method for preparing the 1-O-glycosylcarbamate compound according to any one of claims 1-6, characterized in that, It includes the following steps: (1) In a solvent, under alkaline conditions, amine compounds are reacted with carbon dioxide to undergo a carbamate reaction to obtain a reaction system containing carbamate compounds. (2) After the reaction in step (1) is completed, the solution of halogen glycoside and solvent is added to the reaction system in step (1) to carry out glycosylation reaction and obtain the corresponding 1-O-glycosyl carbamate compound. The reagents for the glycosylation reaction are the carbamic acid compound, the halogenated glycoside, and the solution; or, the reagents for the glycosylation reaction are the carbamic acid compound, the halogenated glycoside, the base, and the solution. Preferably, the reaction conditions and operations for the carbamate reaction in step (1) and the glycosylation reaction in step (2) are as described in claim 2.

8. A compound as shown in Formula 3-85, 9. A pharmaceutical composition, characterized in that, It comprises the compound of formulas 3-85 as described in claim 8, and a pharmaceutically acceptable carrier; 10. The use of a compound of formulas 3-85 as described in claim 8 or a pharmaceutical composition as described in claim 9 in the preparation of an antitumor drug; preferably, the tumor is ROS1-positive advanced non-small cell lung cancer.

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