Glycosidation and alkylation method with participation of benzoiodo-oxalane reagent

Abstract

The invention belongs to the technical field of organic synthesis, and discloses a glycosylation and alkylation method in which a benzoiodo-oxalame reagent participates, and the glycosylation method or the alkylation method comprises the following steps: activating a raw material (a glycosyl donor or an alkylation reagent) under the combined action of the benzoiodo-oxalame reagent and an acid catalyst; and then reacting with a nucleophilic reagent to obtain a corresponding glycosylation product or alkylation product. According to the method disclosed by the invention, the benzoiodo-oxalane reagent is introduced and is combined with the acid catalyst to realize efficient reaction on the basis of not using a noble metal heavy metal catalyst.

Description

Technical Field

[0001] The invention belongs to the technical field related to organic synthesis, and more specifically, relates to a glycosidation and alkylation method involving a benziodooxolane reagent. Background Art

[0002] Hypervalent iodine reagents have rich and varied chemical reactivity. Due to their unique properties, they are widely used in organic synthesis. Hypervalent iodine reagents are environmentally friendly and have properties similar to those of metals. They can replace metal reagents in many reactions and will not pollute the environment, which is in line with the concept of green chemistry. In addition, these hypervalent iodine reagents can be recycled after use, and can be recycled after treatment and then oxidized to regenerate into hypervalent iodine reagents. Therefore, hypervalent iodine reagents have high application value.

[0003] Many types of benzimidazole reagents have been developed and have been widely used in organic synthesis, such as intermediates for the synthesis of certain compounds, as trifluoromethylation reagents, dearomatization, and the construction of carbon heteroatom bonds. These applications have shown the strong potential of this type of reagent. In addition, we found that benzimidazole reagents can also be used in sugar synthesis and alkylation reactions, which expands the application range of benzimidazole reagents.

[0004] Glycosylation is a very important reaction in organic chemistry. Many of the glycosylation reactions currently developed still require expensive metal catalysts, but it is often difficult to find alternative compounds for such metal catalysts. Alkylation is also important in organic synthesis, but the alkylation reactions currently developed usually need to be carried out under strong alkaline conditions, and there is a lack of mild and efficient alkylation methods. Therefore, it is also very important to develop a more effective alkylation method. Summary of the invention

[0005] In view of the above defects or improvement needs of the prior art, the present invention provides a glycosylation and alkylation method involving a benziodooxolane reagent. Both the glycosylation method and the alkylation method are carried out by introducing a benziodooxolane reagent and acting together with an acid catalyst to react with a nucleophilic reagent to obtain a corresponding glycosylation product or alkylation product, thereby solving the problem that the existing glycosylation and / or alkylation methods require the use of precious metals, heavy metals, etc. for efficient reaction.

[0006] To achieve the above object, according to one aspect of the present invention, a glycosylation involving a benziodooxolane reagent is provided, wherein the method comprises: activating a glycosyl donor as shown in formula I under the joint action of a benziodooxolane reagent as shown in formula V and an acid catalyst, and then reacting with a nucleophilic reagent to obtain a glycosylation product as shown in formula VI. The reaction route is as shown in formula 1:

[0007]

[0008] In the glycosyl donor as shown in Formula I, one or more hydroxyl groups on the sugar ring are protected by a glycosyl protecting group, and LG is an alkylthio group, an arylthio group, an aryl selenoyl group, a thiocarboxylate group, an o-alkynyl benzoate group, a pentenoate group, a pentynoate group or a hexynoate group;

[0009] In the benzoiodine oxolane reagent shown in Formula V, R 1 is chlorine, hydroxyl, trimethylsilyloxy, trifluoromethanesulfonyl ester or benzoiodine oxolane oxy, R 2 is methyl or trifluoromethyl;

[0010] Nu in the formula 1 represents a nucleophile, and the nucleophile is selected from primary alcohol, secondary alcohol or carboxylic acid.

[0011] Preferably, the glycosyl donor as shown in Formula I is selected from compounds of any of the following structures:

[0012]

[0013] Preferably, the benziodooxolane reagent having a structural formula as shown in Formula V is selected from compounds of any of the following structures:

[0014]

[0015] Preferably, the molar ratio of the glycosyl donor to the benziodonium oxolane reagent is 1:(0.25-0.5).

[0016] Preferably, the nucleophilic agent is selected from compounds of any of the following structures:

[0017]

[0018] According to another aspect of the present invention, a method for alkylation involving a benziodine oxolane reagent is provided, which method specifically comprises: activating an alkylating agent as shown in formula II under the joint action of a benziodine oxolane reagent as shown in formula V and an acid catalyst, and then reacting with a nucleophilic reagent to obtain an alkylated product as shown in formula VII, and the reaction route is shown in formula II; or, activating an alkylating agent as shown in formula III under the joint action of a benziodine oxolane reagent as shown in formula V and an acid catalyst, and then reacting with a nucleophilic reagent to obtain an alkylated product as shown in formula VIII, and the reaction route is shown in formula III;

[0019]

[0020] The alkylating agent shown in Formula II is a thioether alkylating agent, wherein R3 is an alkyl group, R 4 is an alkyl group or an aryl group;

[0021] The alkylating agent shown in Formula III is a steroidal derivative containing a homoallyl thiocarbonate structure, wherein the steroid is cholesterol, dioscin, dehydroepiandrosterone, pregnenolone, β-sitosterol, stigmasterol; wherein R 5 is phenoxy or methylthio;

[0022] In the benzoiodine oxolane reagent shown in Formula V, R 1 is chlorine, hydroxyl, trimethylsilyloxy, trifluoromethanesulfonyl ester or benzoiodine oxolane oxy, R 2 is methyl or trifluoromethyl;

[0023] Nu in Formula 2 and Formula 3 both represent nucleophiles, and the nucleophiles are selected from primary alcohols, secondary alcohols, phenols or phosphoric acids.

[0024] Preferably, the alkylating agent as shown in Formula II is selected from compounds of any of the following structures:

[0025]

[0026] The alkylating agent as shown in formula III is selected from compounds of any of the following structures:

[0027]

[0028] Preferably, the benziodooxolane reagent having a structural formula as shown in Formula V is selected from compounds of any of the following structures:

[0029]

[0030] Preferably, the molar ratio of the alkylating agent as shown in formula II to the benzoiodine oxolane reagent is 1:(0.25-0.5); the molar ratio of the alkylating agent as shown in formula III to the benzoiodine oxolane reagent is 1:(0.25-0.5).

[0031] Preferably, the nucleophilic agent is selected from compounds of any of the following structures:

[0032]

[0033] In general, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:

[0034] (1) The method of the present invention achieves an efficient reaction without using a noble metal or heavy metal catalyst by introducing a benzoiodine oxolane reagent and acting together with an acid catalyst. At the same time, in the glycosylation reaction, only a substoichiometric amount of the benzoiodine oxolane reagent is introduced to oxidize the leaving group of the sugar ring terminal, and then reacts with an acid to obtain a glycosylated product with an excellent yield. In the alkylation reaction, a substoichiometric amount of the benzoiodine oxolane reagent is introduced, and further, the catalytic effect of the acid, especially for compounds with structures such as those shown in formulas IV-(20-26) and IV-30, can be efficiently alkylated and modified, thereby avoiding the problem of decomposition of certain compounds under strong acid or strong base conditions.

[0035] (2) The benzoiodine oxolane reagent used in the present invention is easy to prepare in large quantities and has low cost.

[0036] (3) The acid used in the present invention has a wide range, which is a common commercially available Bronsted acid or Lewis acid, providing flexible selection for the glycosylation of different substrates.

[0037] (4) The donor used in the present invention can be a glucosinolate or ester glycoside donor with mature synthesis technology, stable properties, and easy preparation and storage.

[0038] In summary, the glycosidation method promoted by the benziodooxolane reagent provided by the present invention effectively overcomes the problems of expensive heavy metals, complex donor structure and difficult preparation, poor donor stability and the like existing in the existing methods, and provides a new and easy-to-implement scheme for the synthesis and alkylation reaction of carbohydrate substances. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0040] Unless otherwise specified, the raw materials or reagents used in the present invention are commercially available. All reagents are commercial grade and used according to the received standards. All moisture-sensitive reactions are carried out in an argon atmosphere. The reaction is monitored by thin layer chromatography (TLC), detected by ultraviolet absorption (254nm), and sprayed with 10% by volume ethanol solution of sulfuric acid, and carbonized at 80-150°C for color development. Flash column chromatography uses silica gel H. 1 H and 13C NMR spectra were recorded on Bruker AV 400 and Bruker AV 600 using deuterated chloroform (CDCl3) as the deuterated reagent. Chemical shifts (δ) are expressed in ppm with tetramethylsilane as the internal standard. Coupling constants (J) are expressed in Hz.

[0041] Unless otherwise specified, the scientific and technical terms and abbreviations used in the present invention have the meanings commonly understood by those skilled in the art. For example, "equivalent" in the present invention refers to the ratio of the amount of each substance involved in the reaction; for another example, the meanings of some abbreviations are as follows:

[0042]

[0043] In the present invention, the trivalent iodine reagent shown in Formula-II is prepared by the following example:

[0044] Step S1, placing an o-iodobenzyl alcohol compound as shown in Formula I and periodic acid or periodate in a reaction container, injecting an acetic acid aqueous solution to obtain a reaction raw material mixed system.

[0045] Step S2: The reaction raw material mixture system of step S1 is stirred for reaction for 4 to 12 hours under heating conditions (110° C.).

[0046] Step S3, after the reaction of step S2 is completed, the reaction system is cooled and directly filtered, and the filter cake is washed with water, acetonitrile and dichloromethane in sequence to obtain part of the target product, and the mother liquor is concentrated and pulped to continue to obtain part of the target product, and the two parts of the target product are combined to obtain all the target products of the final reaction, that is, the benziodooxolane reagent shown in formula II;

[0047] The specific reaction chemical formula involved in the reaction step (2) of the above trivalent iodine reagent is as follows:

[0048]

[0049] Specifically, in the above-mentioned trivalent iodine reagent reaction, R1 in step (2) is selected from methyl or trifluoromethyl, R2 is selected from hydrogen, halogen or methyl; R3 is selected from hydrogen or methyl;

[0050] The molecular structure of the target product obtained by the reaction based on the above scheme is the following formula II-a and / or II-b:

[0051]

[0052] Further, for example, in the present invention, the obtained compound of formula II-a and / or II-b is treated with KOH and a small amount of water in DMSO, or treated with TMSCl and NEt3 in DCM, or treated with TMSOTf in DCM to prepare V-(ah) shown in the glycosylation method and alkylation method of the present invention, wherein the hydroxyl, trifluoromethanesulfonyl, benziodooxolanyl substituted on "I"

[0053] It should be noted that the marks appearing in the preparation process of the above-mentioned trivalent iodine reagent, such as R1, R2, R3, II, etc., are only used to illustrate the preparation instructions of the trivalent iodine reagent. Specifically, can the benzoiodine oxolane reagent prepared by the present research group through the above scheme be used in the embodiments of the present invention? The relevant details of the preparation can also refer to the public information of the present research group on the preparation of the benzoiodine oxolane reagent.

[0054] In the glycosylation method of the present invention, the method is: a glycosyl donor as shown in formula I and a benziodooxolane reagent as shown in formula V are mixed and placed in a low temperature environment, and then an acid is added. After the donor is completely converted, an acceptor nucleophilic reagent (IV) is added to carry out a glycosylation reaction to obtain a glycosylated product as shown in formula VI. The reaction formula is as follows:

[0055]

[0056] In the glycosyl donor as shown in Formula I, one or more hydroxyl groups on the sugar ring are protected by a glycosyl protecting group, and LG is an alkylthio group, an arylthio group, an aryl selenoyl group, a thiocarboxylate group, an o-alkynyl benzoate group, a pentenoate group, a pentynoate group or a hexynoate group;

[0057] In the benziodooxolane reagent as shown in Formula V, R 1 is chlorine, hydroxyl, trimethylsilyloxy, trifluoromethanesulfonyl ester or benzoiodine oxolane oxy, R 2 is methyl or trifluoromethyl.

[0058] Nu in the formula 1 represents a nucleophile, and the nucleophile is selected from primary alcohol, secondary alcohol or carboxylic acid.

[0059] Preferably, in the glycosyl donor as shown in Formula I, the glycosyl protecting groups are each independently selected from an alkyl group, an alkoxy group, an acyloxy group, a siloxy group, a substituted amino group, a cyclic acetal, a cyclic ketal or a glycosyl group.

[0060] Preferably, LG is selected from ethylthio, isopropylthio, p-methylbenzyl, benzylthio, 2-ethylphenylthio, pentynoate, hexynoate, o-alkynylbenzoate, pentenoate or thiocarbonate.

[0061] Preferably, the benziodooxolane reagent as shown in formula V is selected from compounds of any of the following structures:

[0062]

[0063] Preferably, the molar ratio of the glycosyl donor as shown in formula I to the benziodonium oxolane reagent as shown in formula V is 1:(0.25-0.5).

[0064] Preferably, the glycosyl donor as shown in Formula I is selected from compounds of any of the following structures:

[0065]

[0066] Preferably, in the glycosidation method, the nucleophilic reagent (IV) is selected from a compound of any of the following structures:

[0067]

[0068] In the alkylation method of the present invention, the method comprises: activating an alkylating agent as shown in formula II under the joint action of a benziodooxolane reagent as shown in formula V and an acid catalyst, and then reacting with a nucleophilic reagent to obtain an alkylation product as shown in formula VII, and the reaction route is shown in formula II; or, activating an alkylating agent as shown in formula III under the joint action of a benziodooxolane reagent as shown in formula V and an acid catalyst, and then reacting with a nucleophilic reagent to obtain an alkylation product as shown in formula VIII, and the reaction route is shown in formula III;

[0069]

[0070] The alkylating agent thioether alkylating agent shown in Formula II, specifically R 3 is an alkyl group, R 4 When it is an alkyl group, the sulfide alkylating agent is alkoxymethylene sulfide, R 3 is an alkyl group, R 4 When the group is aryl, the sulfide alkylating agent is aryloxymethylene sulfide;

[0071] The thiocarbonate-based reagent in the alkylating agent as shown in Formula III is a steroidal derivative containing a homoallyl thiocarbonate structure, wherein the steroid can be cholesterol, dioscin, dehydroepiandrosterone, pregnenolone, β-sitosterol, stigmasterol; wherein R 5 is phenoxy or methylthio;

[0072] In the benziodooxolane reagent as shown in Formula V, R 1 is chlorine, hydroxyl, trimethylsilyloxy, trifluoromethanesulfonyl ester or benzoiodine oxolane oxy, R 2 is methyl or trifluoromethyl.

[0073] Nu in Formula 2 and Formula 3 both represent nucleophiles, and the nucleophiles are selected from primary alcohols, secondary alcohols, phenols or phosphoric acids.

[0074] Preferably, in the above alkylation method, the benziodooxolane reagent as shown in formula V is selected from compounds of any of the following structures:

[0075]

[0076] Preferably, in the above alkylation method, the molar ratio of the alkylation agent (II or III) to the benziodonium oxolane reagent (V) is 1:(0.25-0.5).

[0077] Preferably, the alkylating agent as shown in Formula II is selected from compounds of any of the following structures:

[0078]

[0079] Preferably, the alkylating agent as shown in formula III is selected from compounds of any of the following structures:

[0080]

[0081] Preferably, in the above alkylation method, the nucleophile (IV) is selected from a primary alcohol, a secondary alcohol, a phenol or a phosphoric acid. The primary alcohol, the secondary alcohol or the carboxylic acid acceptor is selected from a compound of any of the following structures:

[0082]

[0083] In an embodiment of the present invention, in the above-mentioned glycosidation method and alkylation method, the acid is selected from Lewis acid or Bronsted acid; the Lewis acid is selected from trifluoromethanesulfonic anhydride, trimethylsilyl trifluoromethanesulfonate, boron trifluoride ethyl ether or N-trimethylsilyl bistrifluoromethanesulfonimide; the Bronsted acid is selected from trifluoromethanesulfonic acid, N-bistrifluoromethanesulfonimide.

[0084] In an embodiment of the present invention, in the above-mentioned glycosidation method and alkylation method, the molar ratio of acid to nucleophile (IV) is 1:(0.1~1). Specifically, when donors I-01, I-02, I-03, I-04, I-05, I-06, and I-07 are used, the stoichiometric ratio of donor to acid is 1:1. When glycosyl donors I-08, I-09, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-29, and I-30 are used, the stoichiometric ratio of donor to acid is 1:(0.1~0.5).

[0085] In an embodiment of the present invention, in the above-mentioned glycosidation method and alkylation method, the heating temperature involved is -78°C to 30°C, such as -60°C, -40°C, -20°C, -10°C, 0°C, 10°C, 25°C or any interval range composed of these temperature values, preferably -78°C to 25°C, such as -78°C to 0°C, such as -60°C to 0°C, such as -40°C to 0°C, such as -10°C to 0°C. Specifically, the reaction temperature can be selected by those skilled in the art according to common sense.

[0086] The following are specific embodiments:

[0087] Unless otherwise specified, the standard operating procedure for the glycosidation reaction of the embodiment is: the glycosyl donor, the benziodine oxolane reagent, the acceptor and the dried molecular sieve are added. MS was placed in a reaction bottle, sealed with a rubber stopper, and then anhydrous CH2Cl2 (c = 0.05M, calculated based on the equivalent of 1.0 reactants) was added, the reaction system was precooled to 0°C, and then an acid catalyst (20 mol%) was added. After the reaction was complete, the glycosylation product was separated and purified by silica gel column chromatography. In some implementation examples, if the content with special instructions is inconsistent with the standard operating procedure of the reaction, the content with special instructions shall prevail.

[0088] Embodiment 1-30:

[0089] In the glycosidation method of the present invention, the detailed experimental process refers to the above description. The following table provides the yields of glycosyl donors (I) with different structures and benziodooxolane reagents (V) under the action of acid and corresponding reaction conditions.

[0090]

[0091]

[0092] It can be seen from the above examples that different donor structures, such as ethyl glucosinolate, isopropyl glucosinolate, p-methyl phenyl glucosinolate, o-ethyl phenyl glucosinolate, and pentynoate glycoside all show good effects, preferably ethyl glucosinolate, isopropyl glucosinolate, p-methyl phenyl glucosinolate, o-ethyl phenyl glucosinolate, and pentynoate glycoside. More preferably, ethyl glucosinolate can be used. One-quarter equivalent of a benzoiodine oxolane reagent (III-e) and a catalytic amount of an acid can be used to obtain an excellent glycosylation yield.

[0093] Different acid catalysts, such as Bronsted acid or Lewis acid, can play a catalytic role, and the preferred acid catalysts are trimethylsilyl trifluoromethanesulfonate, trifluoromethanesulfonic acid, boron trifluoride ethyl ether, N-trimethylsilyl bistrifluoromethanesulfonimide, etc. In terms of molar percentage, the amount of the acid catalyst is 5-30% of the glycosyl acceptor, more preferably 10%-25%, such as 10-20%.

[0094] Embodiment 31:

[0095]

[0096] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-14 (33.3 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-02 (20.0 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-02 (43.2 mg, 96%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ8.06-7.99(m,4H,Ar-H),7.96-7.92(m,2H,Ar-H),7.89-7. 85(m,2H,Ar-H),7.61-7.23(m,25H,Ar-H),7.02-7.00(m,2H,Ar-H),5.90(t,J=9 .6Hz,1H),5.72(t,J=9.6Hz,1H),5.60(dd,J=9.6,8.0Hz,1H,H-2),5.27(d,J=8. 0Hz,1H,H-1),4.75(d,J=12.0Hz,1H,-CH2Ph),4.66(d,J=12.0Hz,1H,-CH2Ph),4. 61(dd,J=12.0,3.2Hz,1H),4.50(d,J=3.6Hz,1H,H-1'),4.47(s,2H),4.44(dd,J =12.0,4.4Hz,1H),4.13(d,J=11.6Hz,2H,-CH2Ph),4.03(dt,J=10.0,3.6Hz,1H) ,3.93-3.87(m,2H),3.84(dd,J=10.0,2.8Hz,1H),3.73(dd,J=10.0,4.8Hz,1H), 3.64(dd,J=10.0,6.8Hz,1H), 3.59(dd,J=10.0,3.6Hz,1H), 3.32(s,3H,-OCH3).

[0097] Embodiment 32:

[0098]

[0099] According to the standard operating procedure, the raw materials are as follows: donor I-15 (27.9 mg, 0.052 mmol, 1.2 equivalents), benziodine oxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-03 (11.2 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-03 (30.3 mg, 96%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ7.31-7.21(m,13H,Ar-H),7.16-7.12(m,2H,Ar-H),5.46(d,J=4.8Hz,1H,H-1'),4.96(t,J=8.4Hz,1H,H-2),4.75(d,J =10.8Hz,1H,-CH2Ph),4.74(d,J=11.6Hz,1H,-CH2Ph),4.64(d,J=11.2Hz,1H,-CH2Ph),4.60(d,J=12.4Hz,1H,-CH2Ph),4.54-4.49(m,3H), 4.40(d,J=8.0Hz,1H,H-1),4.24(dd,J=4.8,2.4Hz,1H,H-2'), 4.14(dd,J=8.0,1.6Hz,1H),4.02(dd,J=11.2,3.2Hz,1H),3.91-3.86(m,1H) ,3.70-3.56(m,5H),3.45-3.41(m,1H),1.97(s,3H,-COCH3),1.46(s,3H,-CH3),1.39(s,3H,-CH3),1.27(s,3H,-CH3),1.26(s,3H,-CH3).

[0100] Embodiment 33:

[0101]

[0102] According to the standard operating procedure, the raw materials are as follows: donor I-16 (16.7 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-02 (20.0 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-04 (29.5 mg, 95%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 11H NMR (600 MHz, CDCl3) δ 7.39 - 7.26 (m, 15H, Ar-H), 5.19 (t, J = 9.0 Hz, 1H, H-3’), 4.98 (dd, J = 9.0, 7.2 Hz, 1H, H-2’), 4.92 (td, J = 8.4, 5.4 Hz, 1H, H-4’), 4.80 (d, J = 12.0 Hz, 1H, -CH2Ph), 4.79 (d, J = 7.2 Hz, 1H, H-1’), 4.76 (d, J = 12.0 Hz, 1H, -CH2Ph), 4.67 (d, J = 11.4 Hz, 1H, -CH2Ph), 4.60 (d, J = 3.6 Hz, 1H, H-1), 4.58 (d, J = 12.0 Hz, 1H, -CH2Ph), 4.53 (d, J = 11.4 Hz, 1H, -CH2Ph), 4.49 (d, J = 11.4 Hz, 1H, -CH2Ph), 4.06 (d, J = 1.8 Hz, 1H, H-4), 4.02 (dd, J = 12.0, 5.4 Hz, 1H, H-5’a), 3.98 - 3.84 (m, 2H, H-3, H-5), 3.78 (dd, J = 10.2, 3.6 Hz, 1H, H-2), 3.69 (dd, J = 9.6, 6.6 Hz, 1H, H-6a), 3.55 (dd, J = 9.6, 6.0 Hz, 1H, H-6b), 3.35 (s, 3H, -OCH3), 3.24 (dd, J = 12.0, 8.4 Hz, 1H, H-5b), 2.05 (s, 3H, -COCH3), 2.01 (s, 3H, -COCH3), 1.80 (s, 3H, -COCH3). 13 13C NMR (100 MHz, CDCl3) δ 170.2, 170.1, 169.7, 138.6, 138.6, 138.4, 128.6, 128.5, 128.5, 128.1, 127.9, 127.8, 127.8, 127.8, 101.9, 98.7, 78.3, 75.8, 73.8, 73.7, 73.6, 71.6, 71.2, 696, 69.4, 68.9, 62.2, 55.5, 20.9, 20.9, 20.8. HRMS (ESI + ): calc. for C 39 H 46 O 13 [M + Na] + 745.2831, found: 745.2824.

[0103] Example 34:

[0104]

[0105] According to the standard operating procedure, the raw materials are as follows: donor I-17 (27.3 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-01 (20.0 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-05 (39.1 mg, 98%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ7.52-7.20 (m, 15H), 4.97 (d, J = 11.4Hz, 1H), 4.90 (t, J = 9.6Hz, 1H), 4.83 (d, J = 12.0Hz, 1H),4.77-4.67(m,4H),4.60-4.53(m,3H),4.32(d,J=12.0Hz,1H),4.20(d,J=8.4Hz,1H),4.10(dd,J=12.0,4 .2Hz,1H),3.93(d,J=9.6Hz,1H),3.83-3.77(m,3H),3.66(dd,J=10.8,2.4Hz,1H),3.60-3.57(m,1H),3.53( q,J=9.6Hz,1H),3.47-3.42(m,2H),3.40-3.36(m,1H),3.32(s,3H),1.99(s,3H),1.96(s,3H),1.90(s,3H).

[0106] Embodiment 35:

[0107]

[0108] According to the standard operating procedure, the raw materials are as follows: donor I-18 (19.7 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-04 (13.9 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-06 (25.5 mg, 93%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ6.97-6.93(m,2H,Ar-H),6.82-6.79(m,2H,Ar-H),5.54(s,1H,H-1),5.27(t,J=9.2Hz,1H,H-3'),5.21( t, J=9.6Hz, 1H, H-4'), 5.03 (dJ=7.8Hz, 1H, H-1'), 4.96 (ddJ=9.0, 8.4Hz, 1H, H-2'), 4.28 (d, J=5.6Hz, 1H, H-2), 4.20 (dd, J=7 .2,5.6Hz,1H,H-3),3.99(d,J=9.6Hz,1H,H-4'),3.79-3.74(m,4H),3.72(s,3H),3.61(dd,J=10.0,7.6Hz,1H,H-4),2.06(s, 3H,-COCH3),2.00(s,3H,-COCH3),1.99(s,3H,-COCH3),1.51(s,3H,-CH3),1.36(s,3H,-CH3),1.19(d,J=6.0Hz,3H,-CH3-6). 13 C NMR (150MHz, CDCl3) δ170.3, 169.6, 167.3, 155.2, 150.2, 118.0, 114.8, 109.8, 99.6, 96.3, 79.7, 7 8.0,76.2,72.6,72.4,71.5,69.7,64.9,55.8,52.9,28.0,26.6,20.9,20.8,20.7,17.5.HRMS(ESI + ):calc.for C29H38O15[M+Na] + 649.2103,found:649.2103.

[0109] Embodiment 36:

[0110]

[0111] According to the standard operating procedure, the raw materials are as follows: donor I-19 (35.4 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-01 (20.0 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-07 (45.2 mg, 97%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ7.45-7.36(m,5H,Ar-H),7.33-7.21(m,10H,Ar-H),5.37(t,J =10.2Hz,1H),5.31(d,J=3.6Hz,1H),5.04(t,J=10.2Hz,1H),5.00(t,J=9.0Hz,1H) ,4.94(d,J=11.4Hz,1H),4.85(dd,J=10.8,3.6Hz,1H),4.76(d,J=12.0Hz,1H),4.7 3-4.66(m,3H),4.58-4.53(m,2H),4.46(d,J=7.8Hz,1H,H-1'),4.40(d,J=12.0Hz,1 H),4.20(dd,J=12.6,3.6Hz,1H),4.12(dd,J=12.0,2.4Hz,1H),4.05(dd,J=12.0,3 .6Hz,1H),3.97(dd,J=12.6,1.8Hz,1H),3.88-3.82(m,3H),3.81-3.75(m,2H),3.6 2-3.57(m,2H),3.45(dd,J=9.6,3.6Hz,1H),3.35(s,3H),3.14(dt,J=9.6,3.0Hz,1 H),2.09(s,3H),2.06(s,3H),2.02(s,3H),2.00(s,3H),1.96(s,3H),1.93(s,6H).

[0112] Embodiment 37:

[0113]

[0114] According to the standard operating procedure, the raw materials are as follows: donor I-20 (17.4 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-05 (31.5 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-08 (40.6 mg, 94%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 11H NMR (400 MHz, CDCl3) δ 7.94 - 7.87 (m, 4H, Ar-H), 7.73 - 7.67 (m, 4H, Ar-H), 7.55 - 7.46 (m, 2H, Ar-H), 7.41 - 7.29 (m, 10H, Ar-H), 7.02 - 6.94 (m, 2H, Ar-H), 6.70 - 6.61 (m, 2H, Ar-H), 5.71 (t, J = 9.6 Hz, 1H), 5.51 (dd, J = 9.9, 8.0 Hz, 1H), 5.14 (d, J = 8.0 Hz, 1H, H-1’), 5.02 (d, J = 3.2 Hz, 1H), 4.98 (dd, J = 10.4, 8.0 Hz, 1H), 4.56 (dd, J = 10.4, 3.2 Hz, 1H), 4.44 (d, J = 8.0 Hz, 1H, H-1), 4.34 (d, J = 9.6 Hz, 1H), 3.94 (t, J = 9.2 Hz, 1H), 3.88 - 3.79 (m, 2H), 3.68 (s, 3H, -OCH3), 3.55 (m, 1H, H-5’), 2.00 (s, 3H, )-COCH3), 1.89 (s, 3H, -COCH3), 1.86 (s, 3H, -COCH3), 1.09 (s, 9H, -C(CH3)3), 0.85 (d, J = 6.4 Hz, 3H, -CH3). 13 13C NMR (101 MHz, CDCl3) δ 170.6, 170.2, 169.9, 165.6, 165.5, 155.5, 151.6, 135.8, 135.8, 133.9, 133.6, 133.6, 133.3, 129.9, 129.7, 129.7, 129.6, 129.4, 129.2, 128.8, 128.5, 127.8, 127.7, 118.5, 114.6, 100.9, 100.3, 76.3, 75.1, 74.3, 72.3, 71.4, 70.0, 69.1, 68.5, 63.6, 55.7, 27.1, 20.7, 20.7, 20.6, 19.4, 15.8. HRMS (ESI + ): calc. for C 55 H 60 O 16 Si [M+Na] + 1027.3543, found: 1027.3530..

[0115] Example 38:

[0116]

[0117] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-16 (16.7 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-06 (19.5 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-09 (27.8 mg, 91%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.33-7.22(15H,m,Ar-H),5.50(1H,dd,J=2.8,53.2Hz,H-1),5.13(1H,t,J=8.8,8.4Hz),4.94(3H,m),4.80(3H,m,PhCH 2), 4.67(1H,d,J=12.0Hz,PhCH2), 4.53(1H,d,J=10.8Hz,PhCH2), 4.48(1H,d,J=6.8Hz), 4.09(1H,dd,J=4.8,11.6Hz,H-6a), 4.00(1H,dd,J= 1.6,11.2Hz,H-6b),3.95(1H,t,J=9.2,9.6Hz),3.90(1H,m,H-5),3.76(1H,dd,J=3.6,11.2Hz,H-5a'),3.57(1H,t,J=9.6,10.0Hz),3.50(1H ,ddd,J=2.4,9.6,12.0Hz,H-2),3.29(1H,dd,J=8.8,11.6Hz,H-5b'),2.02(3H,s,CH3),2.02(3H,s,CH3),1.99(3H,s,CH3),1.92(3H,s,CH3). 13 C NMR (100MHz, CDCl3) δ170.33, 170.00, 169.46, 138.58, 138.07, 137.76, 128.78, 128.64, 128.32, 128.26, 128.19, 128.10, 127.94, 106.77 ,100.61,81.48,79.51(d,J=20Hz),76.69,76.00,75.34,73.79,72.44,72.40,71.77,70.96,68.91,67.19,20.94,20.91,20.84.HRMS(ESI + ):calc.forC 38 H 43 FNaO 12 [M+Na] +733.2631,found:733.2611.

[0118] Embodiment 39:

[0119]

[0120] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-14 (33.3 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-07 (14.7 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-10 (36.9 mg, 93%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR(400MHz, CDCl3)δδ.057.24(m,28H,Ar-H),5.90(t,J=9.6Hz,1H),5.65(t,J=9.6Hz,1H),5.56-5.43(m,2H),4.77(d,J=7.6Hz,1H,H-1), 4.63(dd,J=12.0,3.2Hz,1H),4.50-4.41(m,2H),4.37-4.22(m,3H),4.17-4.07(m,2H),3.88(dd,J=10.4,3.2Hz,1H),3.65(s,3H,-OCH3).

[0121] Embodiment 40:

[0122]

[0123] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-21 (27.9 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-08 (19.8 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-11 (38.2 mg, 95%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR(400MHz,CDCl3)δ7.31-7.06(m,25H,Ar-H),5.32(dd,J=10.0,8.0Hz,1H,H-2’),5.03(d,J=12.0Hz,1H,-CH2Ph),4.99(d,J=12.4Hz,1H,-CH2Ph),4.91(d,J=11.6Hz,1H,-CH2Ph),4.88(d,J=11.6Hz,1H,-CH2Ph),4.77(d,J=10.0Hz,1H),4.61(d,J=12.0Hz,1H,-CH2Ph),4.59(d,J=3.6Hz,1H,H-1),4.49(d,J=11.6Hz,1H,-CH2Ph),4.45(d,J=11.2Hz,1H,-CH2Ph),4.43(d,J=12.0Hz,1H,-CH2Ph),4.37-4.32(m,2H,H-1’,-CH2Ph),4.20(d,J=11.6Hz,1H,-CH2Ph),4.13(d,J=12.0Hz,1H,-CH2Ph),4.06(dd,J=11.6,4.0Hz,1H),3.90-3.84(m,2H),3.70-3.63(m,2H),3.48(dd,J=10.4,8.4Hz,1H),3.40(dd,J=10.0,2.8Hz,1H),3.38-3.30(m,2H),3.26(s,3H,-OCH3),3.22-3.18(m,1H),2.02(s,3H,-COCH3),1.99(s,3H,-COCH3). 13 C NMR(101MHz,CDCl3)δ170.8,169.8,156.1,139.2,138.8,138.0,136.4,128.6,128.6,128.5,128.3,128.1,128.0,128.0,127.9,127.9,127.7,127.6,127.4,127.1,101.6,98.8,80.6,78.7,78.1,75.1,74.7,73.6,73.5,72.7,72.1,72.0,69.0,68.1,67.0,62.6,55.3,54.6,21.1,21.0.HRMS(ESI + ):calc.for C 53 H 59 NO 14 [M+Na] + 956.3828,found:956.3828.。

[0124] Embodiment 41:

[0125]

[0126] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-22 (31.9 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-09 (15.8 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-12 (38.3 mg, 96%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR(400MHz, CDCl3)δ8.03-7.96(m,4H,Ar-H),7.60-7.37(m,7H,Ar-H),7.32-7.24(m,14 H, Ar-H), 5.72 (d, J = 3.2Hz, 1H, H-1'), 5.52 (dd, J = 10.0, 9.2Hz, 1H, H-3), 4.97 (d, J = 3.2H z,1H,H-4'),4.91(d,J=3.6Hz,1H,H-1),4.86(dd,J=10.0,3.6Hz,1H,H-2),4.76(d,J=11 .2Hz,1H,-CH2Ph),4.65(d,J=12.0Hz,1H,-CH2Ph),4.58(d,J=12.0Hz,1H,-CH2Ph),4.53( d,J=12.0Hz,1H,-CH2Ph),4.52(d,J=11.2Hz,1H,-CH2Ph),4.44(d,J=12.0Hz,1H,-CH2Ph) ),4.40-4.33(m,2H),4.18(dd,J=9.6,3.2Hz,1H),4.03-3.97(m,2H,H-4,H-5),3.93(dd, J=10.0,3.2Hz,1H,H-2'), 3.75(dd,J=10.0,3.2Hz,1H,H-3'), 3.67(d,J=9.6Hz,1H),3.4 4(dd,J=11.2,1.6Hz,1H),3.32(s,3H,-OCH3),2.05(s,3H,-COCH3),1.81(s,3H,-COCH3). 13C NMR (100MHz, CDCl3) δ170.5,170.5,166.0,165.8,138.3,138.3,137.9,133.3,130.1,130.0,129.8,129.8,128.5,128.5,128.5,128.4,128.4,1 28.2,128.0,128.0,127.8,127.6,98.8,96.8,76.4,75.8,73.7,73.5,72 .6,71.2,70.7,70.2,69.0,68.4,68.1,63.3,55.3,21.1,20.9.HRMS(ESI + ):calc.for C 52 H 54 O 15 [M+Na] + 941.3355,found:941.3351.

[0127] Embodiment 42:

[0128]

[0129] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-23 (31.1 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-10 (20.0 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-13 (42.2 mg, 96%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ7.97(d,J=7.2Hz,2H),7.53(t,J=7.2Hz,1H),7.39(t,J=7.8Hz,2H),7.36- 7.24(m,26H),7.24-7.18(m,4H),4.98-4.94(m,3H),4.93-4.89(m,2H),4.82-4.78(m,2H),4.71 -4.66(m,3H),4.63-4.54(m,4H),4.49(d,J=12.0Hz,1H),4.40-4.36(m,1H),4.04-3.96(m,3H), 3.82-3.77(m,2H),3.70(d,J=10.4Hz,1H),3.61-3.53(m,3H),3.43-3.38(m,1H),3.34(s,3H).

[0130] Embodiment 43:

[0131]

[0132] According to the standard operating procedure, the raw materials are as follows: donor I-24 (38.3 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-10 (20.0 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-14 (48.0 mg, 98%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.76-7.69(m,4H),7.47-7.38(m,6H),7.35-7.11(m,30H),4.94(d,J=10.8Hz,2H),4.89( d,J=10.8Hz,1H),4.78-4.67(m,6H),4.64(d,J=12.0Hz,1H),4.58(d,J=3.6Hz,1H),4.47(d,J=11.2Hz,1H),4. 40(d,J=10.8Hz,1H),4.28-4.21(m,2H),4.13-4.05(m,2H),3.96(t,J=9.2Hz,1H),3.81-3.76(m,1H),3.60(dd ,J=10.8,4.8Hz,1H),3.57-3.52(m,1H),3.52-3.39(m,4H),3.39-3.32(m,H),3.30(s,3H),3.30-3.25(m,1H).

[0133] Embodiment 44:

[0134]

[0135] According to the standard operating procedure, the raw materials are as follows: donor I-25 (25.5 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-02 (20.0 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-15 (37.3 mg, 97%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 11H NMR (400 MHz, CDCl3) δ 7.43 - 7.16 (m, 30H, Ar - H), 5.50 (s, 1H), 4.78 (d, J = 12.4 Hz, 1H, -CH2Ph), 4.78 (d, J = 11.6 Hz, 1H, -CH2Ph), 4.70 (d, J = 3.6 Hz, 1H, H - 1), 4.69 - 4.63 (m, 3H, H - 1’, 2× -CH2Ph), 4.59 - 4.51 (m, 3H, 3× -CH2Ph), 4.49 (d, J = 12.0 Hz, 1H, -CH2Ph), 4.47 - 4.41 (m, 2H, 2× -CH2Ph), 4.12 - 4.02 (m, 3H), 3.91 - 3.82 (m, 3H), 3.79 - 3.73 (m, 2H), 3.69 (dd, J = 10.0, 5.6 Hz, 1H), 3.61 (dd, J = 10.0, 6.4 Hz, 1H), 3.35 (s, 3H), 3.32 (dd, J = 10.0, 3.0 Hz, 1H), 3.09 (td, J = 10.0, 4.8 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 139.0, 138.6, 138.6, 138.5, 138.4, 137.7, 129.0, 128.7, 128.5, 128.5, 128.4 128.4, 128.3, 128.2, 128.1, 128.0, 127.9, 127.7, 127.7, 127.6, 127.5, 127.5, 126.2, 102.8, 101.4, 98.5, 78.6, 78.6, 78.4, 76.5, 75.4, 75.0, 73.8, 73.4, 73.4, 72.3, 69.8, 69.3, 68.7, 67.7, 55.5. HRMS (ESI + ): calc. for C 55 H 58 O 11 [M + Na] + 917.3871, found: 917.3884.

[0136] Example 45:

[0137]

[0138] According to the standard operating procedure, donor I-15 (23.1 mg, 0.043 mmol, 1.0 equivalent), benziodooxolane reagent Vf (8.1 mg, 0.011 mmol, 0.25 equivalent), and molecular sieves were added to the reaction bottle, sealed with a rubber stopper, and then anhydrous CH2Cl2 (c = 0.05 M, calculated based on 1.0 equivalent of reactants) was added, the reaction system was precooled to -78 ° C, and then TMSOTf (50 mol%) was added, and then the receptor IV-11 (27.9 mg, 0.052 mmol, 1.2 equivalents) was added after 30 minutes. After the reaction was complete, the glycosylation product VI-16 was separated and purified by silica gel column chromatography. The characterization data of this compound are as follows: 1 H NMR (600MHz, CDCl3) δ7.97-7.93(m,2H),7.92-7.88(m,2H),7.81-7.77(m,2H),7.54-7.48(m,2H),7.43-7.26(m,17H),7.24(ddd,J =8.5,4.1,2.0Hz,2H),7.18-7.13(m,2H),5.86(t,J=9.5Hz,1H),5.49(t,J=9.7Hz,1H),5.37(t,J=9.9Hz,1H),5.02-4.96(m,1H),4 .80-4.74(m,3H),4.66(d,J=11.4Hz,1H),4.53(dd,J=11.4,3.1Hz,2H),4.46(d,J=7.9Hz,1H),4.42(d,J=12.2Hz,1H),4.05-3.98( m,2H),3.73(dd,J=11.4,7.8Hz,1H),3.71-3.61(m,4H),3.47-3.41(m,1H),2.84-2.70(m,2H),2.02(s,3H),1.27(t,J=7.4Hz,3H). 13C NMR (151MHz, CDCl3) δ169.69, 165.86, 165.52, 165.32, 138.30, 138.13, 138.00, 133.62, 133.40,133.31,130.01,129.98,129.83,129.34,129.01,128.88,128.57,128.49,128. 40,128.14,127.99,127.97,127.89,127.75,101.25,83.67,83.03,78.32,77.95,75.28,75.19,75.15,74.35,73.61,73.16,70.80,69.81,68.54,68.52,24.31,21.15,15.04.

[0139] Embodiment 46:

[0140]

[0141] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-14 (25.7 mg, 0.04 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-12 (20.0 mg, 0.033 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and after the reaction is complete, the glycosylation product VI-18 (31.1 mg, 80%) is obtained. The characterization data of the compound are as follows: 11H NMR (600 MHz, CDCl3) δ 8.04 - 8.00 (m, 2H, Ar-H), 7.96 - 7.92 (m, 4H, Ar-H), 7.89 - 7.86 (m, 2H, Ar-H), 7.85 - 7.83 (m, 2H, Ar-H), 7.82 - 7.77 (m, 4H, Ar-H), 7.57 - 7.27 (m, 21H, Ar-H), 5.84 (t, J = 9.6, 1H, H-3), 5.80 (t, J = 9.6, 1H, H-3’), 5.60 (t, J = 9.6 Hz, 1H, H-4’), 5.49 (dd, J = 9.6, 7.8 Hz, 1H, H-2’), 5.43 (dd, J = 9.6, 8.4 Hz, 1H, H-2), 5.32 (d, J = 7.8 Hz, 1H, H-1), 5.31 (t, J = 9.6 Hz, 1H, H-4), 5.05 (d, J = 7.8 Hz, 1H, H-1’), 4.56 (dd, J = 12.0, 3.0 Hz, 1H, H-6a’), 4.41 (dd, J = 12.0, 4.8 Hz, 1H, H-6b’), 4.13 - 4.10 (m, 1H, H-5’), 4.09 - 4.05 (m, 1H, H-5), 4.00 (dd, J = 11.4, 1.8 Hz, 1H, H-6a), 3.95 (dd, J = 11.4, 7.2 Hz, 1H, H-6b), 2.52 (s, 1H, CH), 1.87 - 1.33 (m, 10H). 13 13C NMR (150 MHz, CDCl3) δ 166.2, 165.9, 165.9, 165.6, 165.3, 165.2, 133.6, 133.4, 133.3, 133.3, 133.2, 133.1, 123.0, 129.9, 129.9, 129.9, 129.7, 129.4, 129.1, 128.9, 128.9, 128.9, 128.6, 128.5, 128.5, 128.5, 128.4, 128.4, 128.3, 100.8, 97.1, 84.2, 75.7, 74.3, 73.2, 73.1, 72.4, 72.0, 71.9, 70.1, 69.7, 68.3, 63.2, 38.4, 38.4, 25.0, 22.8. HRMS (ESI + ): calc. for C 69 H 60 O 18 [M + Na] + 1199.3672, found: 1199.3637.

[0142] Example 47:

[0143]

[0144] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-26 (22.7 mg, 0.045 mmol, 1.2 equivalents), benziodooxolane reagent Vf (8.5 mg, 0.011 mmol, 0.3 equivalents), acceptor IV-13 (10.0 mg, 0.037 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-19 (25.0 mg, 95%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ8.57 (s, 1H, NH), 8.02 (ddJ=8.4, 1.2Hz, 2H, Ar-H), 7.98 (dd,J=8.4, 1.2Hz, 2H, Ar-H), 7.90 (dd,J=8.4, 1.2Hz, 2H, Ar-H), 7.59-7. 55(m,1H,Ar-H),7.54-7.50(m,2H,Ar-H),7.42-7.32(m,6H,Ar-H),7.27(d, J=1.2Hz,1H,CH),6.11(t,J=6.6Hz,1H,H-1),5.79(dd,J=6.6,5.4Hz,1H,H- 3'), 5.68 (dJ=4.8Hz, 1H, H-2'), 5.30 (s, 1H, H-1'), 4.77-4.71 (m, 2H, H-4, H-5'a), 4.56 (dd, J=11.4, 4.8Hz, 1H, H-5'b), 4.16 (dt, J=7.8, 5.4Hz, 1H, H- 3),4.04(dd,J=11.4,3.6Hz,1H,H-5a),3.96-3.93(m,1H,H-4),3.71(dd,J= 11.4,4.0Hz,1H,H-5b),2.35-2.25(m,2H,H-2),1.89(d,J=1.2Hz,3H,CH3). 13 C NMR (150MHz, CDCl3) δ166.3, 165.5, 165.5, 163.5, 150.2, 135.5, 133.9, 133.7, 133.5, 129.9, 129.9, 129.8, 129.6, 12 9.0,128.8,128.7,128.6,128.6,111.7,106.5,85.0,82.7,79.6,75.3,71.9,67.6,64.4,60.5,37.4,12.7.HRMS(ESI + ):calc.for C 36 H33 N5O 11 [M+Na] + 734.2069,found:734.2071.

[0145] Embodiment 48:

[0146]

[0147] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-27 (20.0 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (7.2 mg, 0.010 mmol, 0.3 equivalents), acceptor IV-14 (13.0 mg, 0.032 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-20 (22.4 mg, 81%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR(600MHz,CDCl3)δ8.07(d,J=7.2Hz,2H,Ar-H),7.98(d,J=7.2Hz,2H,Ar-H),7.81(d,J=7.2Hz,2H,Ar-H),7.59(t,J=7.2Hz,1H,Ar-H),7.52-7.45(m,3H,Ar-H),7.42-7.36(m,3H,Ar-H),7.27-7.22(m,2H,Ar-H),5.98(d,J=9.6Hz,1H),5.79(dd,J=9.6,6.0Hz,1H),5.72(dd,J=10.2,3.0Hz,1H,H-3),5.67(t,J=9.6Hz,1H,H-4),5.58(dd,J=3.0,1.8Hz,1H,H-2),5.51(s,1H),5.43-5.40(m,1H),5.13(s,1H,H-1),4.67-4.62(m,1H),4.35-4.31(m,1H),4.18-4.13(m,1H,H-5),2.91(dd,J=17.2,3.6Hz,1H),2.79(dd,J=17.2,5.4Hz,1H),2.45-2.31(m,3H),2.29-2.25(m,1H),2.21-2.16(m,1H),1.98(dd,J=15.0,3.6Hz,1H),1.93-1.85(m,2H),1.75-1.63(m,3H),1.60-1.55(m,1H),1.48-1.36(m,3H),1.34(d,J=6.0Hz,3H,CH3-6),1.11-1.05(m,6H,2×CH3),0.93-0.87(m,6H,2×CH3). 13 CNMR(150MHz,CDCl3)δ176.7,169.6,165.9,165.8,165.5,133.7,133.5,133.3,133.2,131.8,130.0,130.0,129.8,129.4,129.2,128.8,128.6,128.5,128.4,97.2,76.7,71.5,71.1,70.3,69.9,67.9,67.7,41.6,37.5,37.0,36.8,33.7,33.1,32.8,30.9,27.6,27.0,24.1,23.0,17.7,16.4,14.1,11.9.HRMS(ESI + ):calc.for C 51 H 58 O 12 [M+Na]+ 885.3820,found:885.3803.

[0148] Embodiment 49:

[0149]

[0150] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-28 (20.0 mg, 0.047 mmol, 1.2 equivalents), benziodooxolane reagent Vf (8.8 mg, 0.012 mmol, 0.3 equivalents), acceptor IV-15 (24.3 mg, 0.039 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-21 (33.1 mg, 86%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.27-7.18(m,10H,Ar-H),7.16-7.13(m,2H,Ar-H),7.0 7-7.04(m,1H,Ar-H),6.52(d,J=2.0Hz,1H,Ar-H),6.42(d,J=2.0Hz,1H,Ar-H) ,5.05(dd,J=3.2,1.6Hz,1H,H-2),4.81-4.76(m,2H),4.62(d,J=11.2Hz,1H, -CH2Ph),4.49(d,J=10.8Hz,1H,-CH2Ph),4.39(d,J=11.2Hz,1H,-CH2Ph),4.1 2(d,J=1.2Hz,1H,H-1),3.91-3.85(m,1H),3.74(dd,J=9.2,3.2Hz,1H,H-3), 3.70-3.63(m,1H,H-5),3.26(t,J=9.6Hz,1H,H-4),2.79(dd,J=16.0,5.6Hz,1 H),2.61(dd,J=16.0,8.8Hz,1H),1.98(s,3H,-COCH3),1.28(s,9H,C(CH3)3) ,1.26(s,18H,2×C(CH3)3),1.25(s,9H,C(CH3)3),1.19(d,J=6.3Hz,3H,CH3). 13C NMR (100MHz, CDCl3) δ176.8, 176.2, 175.7, 175.6, 169.8, 154.9, 150.4, 149.7 ,143.0,142.8,138.6,138.3,136.4,128.5,128.4,128.3,128.1,127.8,127.8 ,124.9,123.7,121.5,111.0,108.8,107.7,98.6,79.9,78.9,78.1,75.5,74. 2,71.9,68.7,68.1,39.4,39.3,39.2,27.4,27.3,27.2,21.10,18.0.HRMS(ESI + ):calc.for C 57 H 70 O 15 [M+Na] + 1017.4607,found:1017.4609.

[0151] Embodiment 50:

[0152]

[0153] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-15 (20.0 mg, 0.037 mmol, 1.2 equivalents), benziodooxolane reagent Vf (7.0 mg, 0.009 mmol, 0.3 equivalents), acceptor IV-16 (12.0 mg, 0.031 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-22 (21.0 mg, 91%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ7.29-7.21(m,13H,Ar-H),7.17-7.13(m,2H,Ar-H),5.29(d,J=4.8Hz,1H),4.91(dd,J=9.2,8.8Hz,1H,H-2),4.75(d,J=11. 2Hz,1H,-CH2Ph),4.74(d,J=11.2Hz,1H,-CH2Ph),4.62(d,J=11.2Hz,1H,-CH2Ph),4.57(d,J=12.0Hz,1H,-CH2Ph),4.54-4.49(m,2H),4.39(d,J= 8.0Hz,1H,H-1),3.70(dd,J=10.8,2.0Hz,1H),3.66-3.58(m,3H),3.47- 3.39(m,2H),2.22-2.10(m,2H),1.99-1.87(m,6H),1.83-1.73(m,2H),1 .54-0.95(m,21H),0.94(s,3H,-CH3),0.87(d,J=6.4Hz,3H,-CH3),0.83(d,J=1.2Hz,3H,-CH3),0.81(d,J=1.2Hz,3H,-CH3),0.63(s,3H,-CH3).

[0154] Embodiment 51:

[0155]

[0156] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-21 (27.9 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-17 (17.8 mg, 0.043 mmol, 1.0 equivalents) acid catalyst TMSOTf (20 mol%), after the reaction is complete, the glycosylation product VI-23 (35.5 mg, 93%) is obtained. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ7.31-7.18(m,13H,Ar-H),7.16-7.13(m,2H,Ar-H),7.09(s ,1H,Ar-H),6.40(s,1H,Ar-H),6.29(s,2H,Ar-H),5.90(d,J=1.2Hz,1H),5.88(d, J=1.2Hz,1H),5.36(dd,J=10.0,8.0Hz,1H,H-2),4.87(d,J=11.6Hz,1H,-CH2Ph), 4.80(d,J=9.6Hz,1H),4.61(d,J=12.0Hz,1H,-CH2Ph),4.53(d,J=11.6Hz,1H,-CH 2Ph),4.50-4.46(m,2H),4.43(d,J=12.0Hz,1H,-CH2Ph),4.37-4.31(m,3H,H-1, 2×-CH2Ph),3.99(dd,J=10.0,9.2Hz,1H),3.86(d,J=2.4Hz,1H,H-4),3.71(s,3H, -OCH3),3.66(s,6H,2×-OCH3),3.57-3.49(m,2H,H-6a,H-6b),3.47-3.41(m,2H,H -5,H-3),2.85-3.75(m,1H),2.69(dd,J=14.4,4.4Hz,1H),1.94(s,3H,-COCH3).

[0157] Embodiment 52:

[0158]

[0159] According to the standard operating procedure of the reaction, the raw materials are as follows: donor I-14 (33.3 mg, 0.052 mmol, 1.2 equivalents), benziodooxolane reagent Vf (9.7 mg, 0.013 mmol, 0.3 equivalents), acceptor IV-18 (21.4 mg, 0.043 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), and the glycosylation product VI-24 (44.5 mg, 96%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 11H NMR (400 MHz, CDCl3) δ 8.03 - 7.98 (m, 2H), 7.96 - 7.92 (m, 2H), 7.89 - 7.85 (m, 2H), 7.83 - 7.77 (m, 2H), 7.54 - 7.45 (m, 3H), 7.42 - 7.30 (m, 7H), 7.27 (d, J = 7.9 Hz, 2H), 5.95 (t, J = 9.7 Hz, 1H), 5.86 (d, J = 8.4 Hz, 1H), 5.76 - 5.65 (m, 2H), 5.21 (t, J = 3.2 Hz, 1H), 4.52 (dd, J = 12.2, 3.0 Hz, 1H), 4.48 - 4.37 (m, 2H), 4.22 (ddd, J = 9.8, 4.6, 3.2 Hz, 1H), 2.12 (d, J = 11.4 Hz, 1H), 2.02 (s, 3H), 1.94 - 1.84 (m, 1H), 1.79 (dd, J = 8.7, 3.2 Hz, 2H), 1.71 (dd, J = 12.2, 4.6 Hz, 1H), 1.59 (d, J = 12.0 Hz, 2H), 1.37 (ddd, J = 27.3, 17.5, 6.5 Hz, 4H), 1.16 (dd, J = 31.5, 8.3 Hz, 3H), 1.06 - 0.91 (m, 4H), 0.88 (s, 8H), 0.79 (t, J = 5.1 Hz, 12H), 0.62 (t, J = 11.0 Hz, 3H), 0.44 (s, 3H), 0.17 (d, J = 12.2 Hz, 1H). 13 13C NMR (100 MHz, CDCl3) δ 175.61, 171.14, 166.23, 165.83, 165.23, 164.91, 137.50, 133.63, 133.49, 133.46, 133.22, 130.11, 129.98, 129.90, 129.74, 128.92, 128.82, 128.58, 128.57, 128.48, 125.95, 92.11, 81.02, 72.97, 70.52, 69.40, 62.89, 55.30, 52.63, 48.26, 47.46, 41.99, 39.25, 39.10, 38.86, 38.35, 37.70, 36.85, 36.07, 32.14, 30.61, 28.34, 28.20, 24.02, 23.64, 23.33, 23.23, 21.46, 21.23, 18.21, 17.11, 16.88, 16.64, 15.59.

[0160] Example 53:

[0161]

[0162] According to the standard operating procedure, the raw materials are as follows: donor I-31 (34.0 mg, 0.050 mmol, 1.5 equivalents), benziodooxolane reagent Vf (10.1 mg, 0.013 mmol, 0.4 equivalents), acceptor IV-33 (10.0 mg, 0.033 mmol, 1.0 equivalents), acid catalyst TMSOTf (20 mol%), after the reaction is complete, the glycosylation product VI-25 (23.8 mg, 88%, α / β=6.5 / 1) is obtained. α configuration: 1 H NMR (600MHz, CDCl3) δ7.91 (dJ=7.2Hz, 2H), 7.76 (d, J=7.8Hz, 2H), 7.71 (dd, J=6.0, 3.4Hz,1H),7.66(s,1H),7.51(t,J=7.4Hz,1H),7.45-7.13(m,20H),5.17(d,J=17. 4Hz, 2H), 5.01 (d, J = 11.1Hz, 1H), 4.95-4.73 (m, 4H), 4.60-4.40 (m, 4H), 4.08-3.86 (m, 2H), 3.77-3.58 (m, 2H), 3.52-3.27 (m, 4H), 1.84 (dd, J = 36.3, 29.8Hz, 2H). β configuration: 1 H NMR (600MHz, CDCl3) δ7.90 (d, J=5.8Hz, 2H), 7.76-7.69 (m, 3H), 7.63 (s, 1H), 7.49 (t, J=7.5Hz, 1H), 7.44-7.39 (m, 2 H),7.40-7.24(m,14H),7.24-7.08(m,4H),5.14(d,J=16.6Hz,2H),4.99(d,J=11.0Hz,1H),4.94(d,J=10.5Hz,1H),4 .82(d,J=10.6Hz,1H),4.76(d,J=11.0Hz,1H),4.61(dd,J=18.4,7.2Hz,1H),4.49(dt,J=26.1,7.6Hz,3H),4.23(dd ,J=55.8,7.0Hz,1H),3.95-3.79(m,1H),3.69(t,J=9.0Hz,1H),3.63-3.49(m,2H),3.48-3.24(m,4H),1.84(m,2H).

[0163] Unless otherwise specified, the standard operating procedure of the alkylation reaction in the embodiment is: the alkylation agent (II) or alkylation agent (III) described in the present invention, the benzoiodine oxolane reagent, the receptor and the dried molecular sieve are added. MS was placed in a reaction bottle, sealed with a rubber stopper, and then anhydrous CH2Cl2 (c = 0.05M, calculated based on the equivalent of 1.0 reactants) was added, the reaction system was precooled to 0°C, and then an acid catalyst (20 mol%) was added. After the reaction was complete, the glycosylation product was separated and purified by silica gel column chromatography. In some implementation examples, if the content with special instructions is inconsistent with the standard operating procedure of the reaction, the content with special instructions shall prevail.

[0164] Embodiment 54:

[0165]

[0166] According to the standard operating procedure, the raw materials are as follows: thioether II-a (18.68 mg, 0.11 mmol, 1.2 equivalents), benziodooxolane reagent Vf (20.93 mg, 0.028 mmol, 0.3 equivalents), receptor IV-19 (30.0 mg, 0.092 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-1 (40.0 mg, 97%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.40-7.35(m,2H,Ar-H),7.26-7.11(m,8H,Ar-H),5.48(s,1H,Ph-H),4.88(d,J=1.6,5.2Hz,2H,OC H2 O),4.82-4.76(m,2H,H-1,H-2),4.52(dd,J=11.6,13.6Hz,2H,Bn-H),4.28-4.19(m,2H,H-6,H-3),3.80(td,J= 4.8,10Hz,1H,H-5),3.69(t,J=10Hz,1H,H-6),3.59(t,J=9.6Hz,1H,H-4),3.32(s,3H,OMe),2.00(s,3H,OAc). 13 CNMR (100MHz, CDCl3) δ192.5,170.5,137.9,137.3,134.6,129.9,129.2,129.1,128.7,128.4,128.3,128.3,128.1,127.9,127.6 ,126.3,101.8,97.7,97.0,96.3,95.1,82.5,81.5,73.4,72.6,71.8,71.0,70.6,70.4,69.5,69.1,62.7,62.4,55.4,55.3,21.1.

[0167] Embodiment 55:

[0168]

[0169] According to the standard operating procedure, the raw materials are as follows: thioether II-a (28.61 mg, 0.17 mmol, 2.4 equivalents), benziodooxolane reagent Vf (32.06 mg, 0.043 mmol, 0.6 equivalents), receptor IV-20 (20.0 mg, 0.071 mmol, 1.0 equivalents), acid catalyst Tf2O (10 mol%), and the target product VII-2 (31.7 mg, 86%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.37-7.33(m,2H,Ar-H),7.28-7.05(m,13H,Ar-H),5.44(s,1H,PhC H ),4.88-4.84(m,3H,BnOC H2 O), 4.82(t, J=6.4Hz,1H,BnOC H2 O),4.75(d,J=3.6Hz,1H,H-1),4.64(d,J=12.0Hz,1H,Bn-H),4.55(d,J=12.0Hz,1H,Bn-H),4.49(t,J=12.0Hz,2H,Bn-H),4.18(dd,J=4.8,10.0H z,1H,H-6a),4.13(t,J=9.2Hz,1H,H-4),3.76(td,J=4.8,10Hz,1H,H-5) ,3.68-3.60(m,2H,H-6b,H-2),3.50(t,J=9.6Hz,1H,H-3),3.30(s,3H,OC H3 ). 13 C NMR (101MHz, CDCl3) δ138.0,137.7,137.4,129.1,128.6,128.4,128.4,128.0,127.9,127. 8,127.6,126.3,101.9,99.9,96.0,95.5,81.7,79.0,74.3,69.8,69.6,69.2,62.5,55.4..

[0170] Embodiment 56:

[0171]

[0172] According to the standard operating procedure, the raw materials are as follows: thioether II-a (14.12 mg, 0.084 mmol, 1.5 equivalents), benziodooxolane reagent Vf (16.87 mg, 0.022 mmol, 0.4 equivalents), receptor IV-11 (30.0 mg, 0.056 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-3 (34.5 mg, 94%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.95-7.88(m,4H,Ar-H),7.82-7.77(m,2H,Ar-H),7.52-7.46(m,2H,Ar-H),7.43-7.32(m,5H,Ar-H),7.28-7.21(m,7H,Ar- H),5.86(t,J=9.2Hz,1H,H-3),5.60(t,J=10.0Hz,1H,H-4),5.53(t,J=10.0Hz,1H,H-2),4.78(d,J=10.0Hz,1H,H-1),4.76(d,J=6.8Hz,1H,BnOC H2 O), 4.73(d, J=6.8Hz,1H,BnOC H2 O),4.53(s,2H,Bn-H),3.97(td,J=3.6,8Hz,1H,H-5),3.85-3.77(m,2H,H-6a,H-6b),2.83(m,2H,SC H2 CH3),1.25(t,J=7.6Hz,3H,SCH2C H3 ). 13 C NMR (101MHz, CDCl3) δ166.0,165.4,165.3,137.8,133.5,133.4,133.3,130.0,129.9,129.9,129.4,129. 2,129.1,128.6,128.5,128.4,128.1,127.8,95.0,83.9,77.9,74.6,70.8,69.7,69.5,66.8,24.2,15.0.

[0173] Embodiment 57:

[0174]

[0175] According to the standard operating procedure, the raw materials are as follows: thioether II-a (11.40 mg, 0.068 mmol, 1.2 equivalents), benziodooxolane reagent Vf (12.77 mg, 0.017 mmol, 0.3 equivalents), receptor IV-21 (20.0 mg, 0.056 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-4 (25.4 mg, 95%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ7.45-7.41(m,2H,Ar-H),7.33-7.19(m,8H,Ar-H),5.54(s,1H,PhC H ),5.07(t,J=9.0Hz,1H,H-2),4.97(d,J=6.6Hz,1H,BnOC H2 O), 4.81(d, J=6.6Hz,1H,BnOC H2 O),4.57(d,J=11.4Hz,1H,Bn-H),4.52(d,J=11.4Hz,1H,Bn-H),4.49(d,J=10.2Hz,1H,H-1),4.36(dd,J=5.4,10.8Hz,1H,H-6a),4.05 (t,J=9.0Hz,1H,H-3),3.76(t,J=10.2Hz,1H,H-6b),3.69(t,J=9.6Hz,1H,H-4),3.51(td,J=4.8,9.6Hz,1H,H-5),2.74-2.66(m,2H,SC H2 CH3),2.02(s,3H,OAc),1.25(t,J=7.2Hz,3H,SCH2C H3 ). 13 C NMR (150MHz, CDCl3) δ169.8,137.7,137.1,129.2,128.5,128.4,127.8,127.8,1 26.2,101.7,95.0,84.5,81.0,77.0,71.5,70.8,69.6,68.7,24.2,21.1,14.9..

[0176] Embodiment 58:

[0177]

[0178] According to the standard operating procedure, the raw materials are as follows: thioether II-a (13.16 mg, 0.078 mmol, 1.2 equivalents), benziodooxolane reagent Vf (14.74 mg, 0.020 mmol, 0.3 equivalents), receptor IV-22 (30.0 mg, 0.065 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-5 (27.5 mg, 73%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.97-7.91(m,4H,Ar-H),7.55-7.46(m,2H,Ar-H),7.41-7.30(m,4H,Ar-H),7.29-7.21(m,3H,Ar-H),7.16-7 .11(m,2H,Ar-H),5.75(t,J=9.6Hz,1H,H-3),5.46(t,J=10.0Hz,1H,H-2),4.79(d,J=10.0Hz,1H,H-1),4.75(d,J=6.8Hz,1H,BnOC H2 ),4.70(d,J=6.8Hz,1H,BnOC H2 ),4.46(d,J=12.0Hz,1H,Bn-H),4.33(d,J=12.8Hz,1H,Bn-H),4.32(t,J=9.6Hz,1H,H-4),4.19(d,J=9.6Hz,1H,H-5),3.76(s,3H,COOC H3 ),2.83-2.73(m,2H,SC H2 CH3),1.27(t,J=7.6Hz,3H,SCH2C H3 ). 13 C NMR (150MHz, CDCl3) δ168.0,165.8,165.4,137.3,133.4,133.4,130.0,129.9,129.3,129. 2,128.5,128.5,128.4,127.7,95.6,84.3,78.9,76.6,75.2,70.4,70.3,52.9,24.4,14.8.

[0179] Embodiment 59:

[0180]

[0181] According to the standard operating procedure, the raw materials are as follows: thioether II-a (53.86 mg, 0.32 mmol, 5.0 equivalents), benziodooxolane reagent Vf (24.14 mg, 0.032 mmol, 0.5 equivalents), receptor IV-23 (20.0 mg, 0.064 mmol, 1.0 equivalents), acid catalyst Tf2O (10 mol%), after the reaction is complete, the target product VII-6 (26.3 mg, 74%) is obtained. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.39-7.35(m,2H,Ar-H),7.31-7.15(m,11H,Ar-H),7.12-7.07(m,2H,Ar-H),5.46(s,1H,Ph-H),5.02(d,J=6.8Hz,1H,BnOC H2 O), 4.97-4.89(m,3H,BnOC H2 O+Bn-H),4.79(d,J=11.6Hz,1H,Bn-H),4.63(d,J=12Hz,1H,Bn-H),4.53(s,2H,BnOC H2 O),4.48(d,J=9.6Hz,1H,H-1),4.260(dd,J=4.4,10Hz,1H,H-6),3.94(t,J=8.8Hz,1H,H-3),3.69(t,J=10. 4Hz,1H,H-6),3.59(q,J=9.6,18.4Hz,2H,H-2,H-4),3.42(td,J=4.8,9.6Hz,1H,H-5),2.72-2.63(m,2H,SC H2 CH3),1.21(t,J=7.2Hz,3H,SCH2C H3 ). 13 C NMR (100MHz, CDCl3) δ138.38,138.26,137.63,130.28,129.59,129.53,129.20,128.90,128.84,128.79,128.58,128.37,128 .29,128.17,128.07,126.70,102.13,96.71,96.06,86.06,81.36,79.55,78.33,71.27,70.98,70.57,69.25,25.16,15.36.

[0182] Embodiment 60:

[0183]

[0184] According to the standard operating procedure, the raw materials are as follows: thioether II-a (10.12 mg, 0.060 mmol, 1.2 equivalents), benziodooxolane reagent Vf (11.34 mg, 0.015 mmol, 0.3 equivalents), receptor IV-24 (30.0 mg, 0.050 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-7 (26.9 mg, 74%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.97-7.92(m,2H,Ar-H),7.90-7.85(m,2H,Ar-H),7.79-7.74(m,2 H,Ar-H),7.52-7.45(m,2H,Ar-H),7.40-7.30(m,7H,Ar-H),7.27-7.21(m,7H,Ar-H),7. 07(d,J=8.0Hz,2H,Ar-H),5.83(t,J=9.2Hz,1H,H-3),5.53(t,J=9.6Hz,1H,H-4),5.42( t,J=9.6Hz,1H,H-2),4.94(d,J=10.0Hz,1H,H-1),4.77-4.71(q,J=6.8,10.0Hz,2H,BnOC H2 ),4.53(t,J=12.4Hz,2H,Bn-H),3.96(m,1H,H-5),3.84-3.75(m,2H,H-6a,H-6b),2.31(s,3H,C H3 ). 13 C NMR (150MHz, CDCl3) δ166.0,165.3,165.2,138.7,137.8,133.8,133.5,133.4,133.3,130.0,129.9,129.9,129.9 ,129.5,129.09,129.0,128.6,128.5,128.4,128.1,127.8,95.0,86.4,77.9,74.6,70.8,69.6,69.5,66.8,21.3..

[0185] Example 61:

[0186]

[0187] According to the standard operating procedure, the raw materials are as follows: thioether II-a (13.25 mg, 0.079 mmol, 1.2 equivalents), benziodooxolane reagent Vf (14.84 mg, 0.020 mmol, 0.3 equivalents), receptor IV-25 (35.0 mg, 0.066 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-8 (34.2 mg, 80%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ8.07-8.03(m,2H,Ar-H),7.54-7.50(m,1H,Ar-H),7.40-7.36(m,2H,Ar-H),7.35-7.20(m,13H,Ar- H),7.10-7.05(m,2H,Ar-H),5.66(dd,J=8.4,10.2Hz,1H,H-2),4.92(d,J=11.4Hz,1H,Bn-H),4.74(d,J=6.6Hz,1H,BnOC H2 ),4.67(d,J=7.2Hz,1H,BnOC H2 ),4.61(d,J=8.4Hz,1H,H-1),4.60(d,J=12.0Hz,1H,Bn-H),4.48(d,J=12.0Hz,1H,Bn-H),4.44(d,J=12.0Hz,2H,Bn-H) ,4.39(d,J=12.0Hz,1H,Bn-H),4.01(dd,J=3.0,10.2Hz,1H,H-3),3.99-3.95(m,2H,H-4,H-5),3.70(t,J=6.6Hz,1H,OC H2 CH2N3), 3.67-3.61(m,3H,OC H2 C H2 N3),3.37(m,1H,H-6a),3.24(dt,J=4.8,13.2Hz,1H,H-6b). 13 C NMR (150MHz, CDCl3) δ165.5, 138.4, 137.9, 137.5, 133.2, 130.1, 129.9, 128.6, 128.5, 128.4, 128. 4,128.0,127.8,127.6,101.6,93.2,77.2,74.7,74.0,73.7,73.5,71.4,69.8,68.6,67.6,50.8.

[0188] Embodiment 62:

[0189]

[0190] According to the standard operating procedure, the raw materials are as follows: thioether II-a (15.11 mg, 0.090 mmol, 1.2 equivalents), benziodooxolane reagent Vf (16.93 mg, 0.022 mmol, 0.3 equivalents), receptor IV-26 (20.0 mg, 0.075 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-9 (25.6 mg, 88%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ8.88 (s, 1H, NH), 7.48 (s, 1H, NC H C),7.38-7.28(m,5H,Ar-H),6.19(t,J=6.0Hz,1H,H-1),4.84(s,2H,BnOC H2 ),4.63(d,J=12.0Hz,1H,Bn-H),4.60(d,J=12.0Hz,1H,Bn-H),4.11(dt,J=5.4,10.2Hz,1H,H-3),4.00(dt,J=3.0,6.0Hz,1H,H-4),3.86(dd,J=3 .0,10.8Hz,1H,H-5a),3.78(dd,J=3.0,10.8Hz,1H,H-5b),2.39(dt,J=6.0,14.4Hz,1H,H-6a),2.26(dt,J=6.0,14.4Hz,1H,H-6b),1.88(s,3H,C H3 ). 13 CNMR (150MHz, CDCl3) δ163.8, 150.3, 137.5, 135.6, 128.7, 128.2, 127.9, 111.1, 95.4, 84.9, 83.2, 70.5, 67.2, 60.4, 38.0, 12.8.

[0191] Embodiment 63:

[0192]

[0193] According to the standard operating procedure, the raw materials are as follows: thioether II-a (25.73 mg, 0.15 mmol, 1.5 equivalents), benziodooxolane reagent Vf (30.75 mg, 0.041 mmol, 0.4 equivalents), receptor IV-27 (20.0 mg, 0.10 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-10 (26.8 mg, 83%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ7.26-7.16(m,5H,Ar-H),7.06(d,J=2.0Hz,1H,Ar-H),6.82(dd,J=2.4,8.4Hz,1H,Ar-H),6.76(d,J=8.0Hz,1H,Ar-H),5.26(s,2H,PhCH2OC H2 ),4.69(s,2H,PhC H2 OCH2), 3.78(s,3H,COOC H3 ),3.57(s,3H,OC H3 ),3.46(s,2H,PhC H2 CO2Me). 13 CNMR (100MHz, CDCl3) δ172.3, 149.1, 146.6, 137.5, 128.5, 128.1, 127.9, 126.7, 123.4, 117.9, 111.9, 93.7, 70.3, 56.1, 52.1, 40.6.

[0194] Embodiment 64:

[0195]

[0196] According to the standard operating procedure, the raw materials are as follows: thioether II-a (13.36 mg, 0.079 mmol, 1.2 equivalents), benziodooxolane reagent Vf (14.96 mg, 0.020 mmol, 0.3 equivalents), receptor IV-28 (20.0 mg, 0.066 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-11 (26.9 mg, 96%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ7.36-7.25(m,5H),5.70(d,J=2.4Hz,1H),4.82(d,J=7.2Hz,1H),4.80(d,J=7.2 Hz,1H),4.61(s,2H),3.64-3.57(m,1H),2.83-2.76(m,1H),2.54(ddd,J=1.8,4.8,13.8Hz,1H),2.47- 2.35(m,3H),2.15-2.07(m,1H),2.03-1.97(m,1H),1.95(dt,J=4.2,13.8Hz,1H),1.83(dt,J=3.0,13 .2Hz,1H),1.77-1.70(m,2H),1.66-1.61(m,2H),1.55-1.52(m,1H),1.24-1.15(m,6H),0.87(s,3H).

[0197] Embodiment 65:

[0198]

[0199] According to the standard operating procedure, the raw materials are as follows: thioether II-b (9.40 mg, 0.047 mmol, 1.2 equivalents), benziodooxolane reagent Vf (8.94 mg, 0.012 mmol, 0.3 equivalents), receptor IV-29 (20.0 mg, 0.039 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-12 (25.4 mg, 98%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.87-7.83(m,2H,Ar-H),7.82-7.78(m,2H,Ar-H),7.76-7.72(m,2H,A r-H),7.41-7.34(m,2H,Ar-H),7.32-7.21(m,5H,Ar-H),7.18-7.11(m,2H,Ar-H),7.05-7.00 (m,2H,Ar-H),6.67-6.62(m,2H,Ar-H),6.01(t,J=9.6Hz,1H,H-3),5.56(t,J=9.6Hz,1H,H-4 ),5.16(dd,J=3.6,9.6Hz,1H,H-2),5.13(d,J=3.6Hz,1H,H-1),4.63(q,J=6.8,9.2Hz,2H,OC H2 O), 4.36(s,2H,PhC H2O),4.11(ddd,J=2.8,4.4,10.4Hz,1H,H-5),3.72-3.65(m,2H,H-6a,H-6b),3.64(s,3H,PhOC H3 ),3.36(s,3H,-OC H3 ). 13 C NMR (150MHz, CDCl3) δ166.0,165.4,133.5,133.2,130.1,130.0,129.8,129.7,129.4,12 9.2,128.6,128.6,128.4,113.9,97.3,94.8,72.3,70.8,69.4,69.2,68.8,66.1,55.8..

[0200] Embodiment 66:

[0201]

[0202] According to the standard operating procedure, the raw materials are as follows: thioether II-c (10.97 mg, 0.071 mmol, 1.2 equivalents), benziodooxolane reagent Vf (13.40 mg, 0.018 mmol, 0.3 equivalents), receptor IV-29 (30.0 mg, 0.059 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-13 (35.3 mg, 97%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.87-7.82(m,2H),7.78-7.71(m,4H),7.40-7.34(m,2H),7.32-7.20(m,4H),7.19-7.0 6(m,4H),6.88-6.80(m,3H),5.99(t,J=9.6Hz,1H,H-3),5.45(t,J=10.0Hz,1H,H-4),5.17(d,J=6.8Hz,1H,OC H2 O),5.13(dd,J=3.6,10.0Hz,1H,H-2),5.09(m,2H,H-1,OC H2 O),4.10(dt,J=4.0,10.0Hz,1H,H-5),3.80-3.72(m,2H,H-6a,H-6b),3.30(s,3H,O Me ). 13C NMR (150MHz, CDCl3) δ166.0, 165.9, 165.4, 157.2, 133.5, 133.5, 133.2, 130.1, 129.9, 129.8, 129.6, 129.4 ,129.2,129.1,128.5,128.5,128.4,122.1,116.4,116.3,97.1,93.9,72.2,70.7,69.6,68.9,67.4,55.7.

[0203] Embodiment 67:

[0204]

[0205] According to the standard operating procedure of the reaction, the raw materials are as follows: thioether II-d (11.96 mg, 0.071 mmol, 1.2 equivalents), benziodooxolane reagent Vf (13.40 mg, 0.018 mmol, 0.3 equivalents), receptor II-30 (30.0 mg, 0.059 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-14 (28.9 mg, 89%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.86-7.79(m,4H,Ar-H),7.76-7.71(m,2H,Ar-H),7.41-7.34 (m,2H,Ar-H),7.31-7.11(m,7H,Ar-H),6.00(t,J=9.6Hz,1H,H-3),5.52(t,J=10.0 Hz,1H,H-4),5.14(dd,J=4,9.6Hz,1H,H-2),5.12(d,J=4Hz,1H,H-1),4.52(q,J=6. 4,15.2Hz,2H,H-6a,H-6b),4.09(dt,J=4.0,10.8Hz,1H,H-5),3.61(d,J=4Hz,2H,OC H2 O), 3.35(s,3H,OC H3 ),3.19(s,3H,-CH2OC H3 ). 13 C NMR (150MHz, CDCl3) δ166.0,165.4,133.5,133.5,133.2,130.1,129.9,129.8,129.4 ,129.2,128.6,128.5,128.4,97.2,97.0,72.3,70.8,69.4,68.8,66.0,55.8,55.5.

[0206] Embodiment 68:

[0207]

[0208] According to the standard operating procedure, the raw materials are as follows: thioether II-d (14.14 mg, 0.084 mmol, 1.5 equivalents), benziodooxolane reagent Vf (16.87 mg, 0.022 mmol, 0.4 equivalents), receptor IV-11 (30.0 mg, 0.056 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-15 (24.3 mg, 75%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.95-7.88(m,4H,Ar-H),7.81-7.77(m,2H,Ar-H),7.52-7.4 6(m,2H,Ar-H),7.43-7.22(m,7H,Ar-H),5.86(t,J=9.2Hz,1H,H-3),5.56(t,J=9. 6Hz,1H,H-4),5.52(t,J=9.6Hz,1H,H-2),4.79(d,J=10.0Hz,1H,H-1),4.61(q,J= 6.4,12Hz,2H,H-6a,H-6b),3.97(dt,J=4.0,10.0Hz,1H,H-5),3.77-3.71(m,2H,OC H2 O),3.29(s,3H,-OC H3 ),2.84-2.71(m,2H,-SC H2 CH3),1.26(t,J=7.2Hz,3H,-SCH2C H3 ). 13 C NMR (150MHz, CDCl3) δ166.0, 165.4, 165.3, 133.5, 133.4, 133.3, 130.0, 129.9, 129.9, 129.4, 129. 1,129.0,128.6,128.5,128.4,97.0,83.8,78.0,74.5,70.8,69.7,66.7,55.5,29.8,24.3,15.0.

[0209] Embodiment 69:

[0210]

[0211] According to the standard operating procedure, the raw materials are as follows: thioether II-d (10.08 mg, 0.060 mmol, 1.2 equivalents), benziodooxolane reagent Vf (11.30 mg, 0.015 mmol, 0.3 equivalents), receptor IV-19 (16.2 mg, 0.050 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), after the reaction is complete, the target product VII-16 (13.9 mg, 76%) is obtained. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ7.48-7.42(m,2H,Ar-H),7.37-7.30(m,3H,Ar-H),5.53(s,1H,Ph-H),4.92(s,1H,OC H2 O), 4.86-4.80(m,2H,OC H2 O,H-2),4.70(d,J=6.6Hz,1H,H-1),4.27(dt,J=1.8,10.2Hz,1H,H-6a),4.18(t,J=9.2Hz,1H,H-3),3.84(td,J=4.8,1 0.8Hz,1H,H-5),3.75(t,J=10.2Hz,1H,H-6b),3.61(t,J=9.6Hz,1H,H-4),3.38(s,3H),3.33(s,3H),2.12(s,3H,OCOC H3 ). 13 C NMR (150MHz, CDCl3) δ170.5,137.3,129.2,128.4,126.2,101.7,97.8,97.2,81.6,73.0,72.7,69.1,62.4,55.8,55.4,21.1.

[0212] Embodiment 70:

[0213]

[0214] According to the standard operating procedure, the raw materials are as follows: thioether II-d (10.05 mg, 0.060 mmol, 1.2 equivalents), benziodooxolane reagent Vf (11.26 mg, 0.015 mmol, 0.3 equivalents), receptor IV-26 (13.3 mg, 0.050 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-17 (11.4 mg, 73%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ8.78 (s, 1H, N H),7.53(s,1H),6.20(t,J=6.0Hz,1H,H-1),4.70(dt,J=4.8,10.8Hz,2H,OC H2 O),4.27(dd,J=5.4,11.4Hz,1H,H-3),4.02(m,1H,H-4),3.85(dt,J=2.4,10.8Hz,1H,H-5a),3.73(dt,J=2.4,10.8Hz,1H,H-5b),3.38(s,3H,OC H3 ),2.45-2.28(m,2H,H-2a,H-2b),1.89(s,3H,C H3 ). 13 C NMR (150MHz, CDCl3) δ163.7, 150.3, 135.6, 111.1, 96.9, 84.9, 83.2, 66.9, 60.3, 55.8, 38.1, 12.8.

[0215] Embodiment 71:

[0216]

[0217] According to the standard operating procedure, the raw materials are as follows: thioether II-d (10.09 mg, 0.060 mmol, 1.2 equivalents), benziodooxolane reagent Vf (11.30 mg, 0.015 mmol, 0.3 equivalents), receptor IV-16 (31.3 mg, 0.050 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-18 (28.5 mg, 86%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ7.26-7.24(m,1H),7.14(t,J=1.8Hz,1H),7.10(d,J=8.4 Hz,1H),6.56(t,J=2.4Hz,1H),6.47(t,J=2.4Hz,1H),4.86(d,J=7.8Hz,1H),4. 51(d,J=7.2Hz,1H),4.29(d,J=7.2Hz,1H),3.96-3.91(m,1H),3.12(s,3H),2. 92(dd,J=5.4,16.2Hz,1H),2.64(dd,J=9.0,16.2Hz,1H),1.35-1.29(m,36H).

[0218] Embodiment 72:

[0219]

[0220] According to the standard operating procedure of the reaction, the raw materials are as follows: thioether II-a (13.36 mg, 0.079 mmol, 1.2 equivalents), benzoiodine oxolane reagent Vf (14.96 mg, 0.020 mmol, 0.3 equivalents), receptor IV-28 (20.0 mg, 0.066 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-19 (16.3 mg, 71%) is obtained after the reaction is complete. 1 H NMR (400MHz, CDCl3) δ5.72 (d, J = 2.0 Hz, 1H), 4.68 (d, J = 6.8 Hz, 1H), 4.66 (d, J = 6 .8Hz,1H),3.58-3.48(m,1H),3.35(s,3H),2.84-2.75(m,1H),2.57(ddd,J=2.4, 4.8,14.0Hz,1H),2.49-2.34(m,3H),2.11(m,1H),2.03-1.91(m,2H),1.86-1.7 9(m,1H),1.79-1.69(m,2H),1.61-1.47(m,3H),1.24-1.15(m,6H),0.87(s,3H). 13 C NMR (150MHz, CDCl3) δ220.5,201.1,166.2,126.1,95.2,75.7,55.5,50.2,48.0 ,45.9,45.9,44.5,39.7,38.7,36.4,35.8,30.8,28.7,24.3,20.7,17.5,13.9..

[0221] Embodiment 73:

[0222]

[0223] According to the standard operating procedure of the reaction, the raw materials are as follows: thioether II-e (18.09 mg, 0.071 mmol, 1.2 equivalents), benziodooxolan reagent Vf (13.40 mg, 0.018 mmol, 0.3 equivalents), receptor IV-29 (30.0 mg, 0.059 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-20 (37.0 mg, 98%) is obtained after the reaction is complete. 1H NMR (400MHz, CDCl3) δ7.86-7.79(m,4H,Ar-H),7.76-7.71(m,2H,Ar-H),7.40-7.34(m,2H,Ar-H),7.32- 7.11(m,7H,Ar-H),6.00(t,J=10.0Hz,1H,H-3),5.50(t,J=10.0Hz,1H,H-4),5.14(dd,J=4,9.6Hz,1H,H -2),5.12(d,J=4Hz,1H,H-1),4.57(q,J=6.8,16Hz,2H,H-6a,H-6b),4.09(ddd,J=2.8,4.4,10.4Hz,1H, H-5),3.66-3.58(m,2H),3.50-3.43(m,2H),3.35(s,3H,OMe),0.75-0.69(m,2H),-0.16(s,9H,-CH3×3). 13 C NMR (150MHz, CDCl3) δ166.0,165.3,133.5,133.2,130.1,129.9,129.8,129.4,129. 2,128.5,128.4,97.2,95.4,72.3,70.8,69.4,68.9,66.1,65.4,55.7,18.1,-1.3..

[0224] Embodiment 74:

[0225]

[0226] According to the standard operating procedure, the raw materials are as follows: thioether II-f (18.71 mg, 0.090 mmol, 1.2 equivalents), benziodooxolane reagent Vf (16.93 mg, 0.022 mmol, 0.3 equivalents), receptor IV-26 (20.0 mg, 0.075 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-21 (25.6 mg, 97%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ8.91 (s, 1H), 7.55 (dd, J = 1.6, 9.2Hz, 1H), 6.22 (m, 1H), 4.66-4.61 (m, 0.55H), 4.60-4.56 (m, 0. 45H),4.38-4.31(m,0.55H),4.28-4.22(m,0.45H),4.09(dd,J=2.8,11.2Hz,0.45H),4.07-4.02(m,1H),3.95(dd,J=2 .4,11.6Hz,0.55H),3.92-3.86(m,0.45H),3.85-3.79(m,0.55H),3.76(m,0.55H),3.61-3.50(m,1.45H),2.45-2.37( m,1H),2.33-2.21(m,1H),1.91(d,J=1.2Hz,1.35H),1.88(d,J=1.2Hz,1.65H),1.84-1.73(m,2H),1.61-1.49(m,4H). 13 C NMR (150MHz, CDCl3) δ164.0,164.0,150.4,135.7,135.5,111.1,111.0,100.2,99.4,85.1,84.9,83.6, 83.3,67.2,66.7,63.6,63.2,61.0,60.7,38.3,38.1,30.8,30.8,25.3,25.3,20.3,20.0,12.7,12.5.

[0227] Embodiment 75:

[0228]

[0229] According to the standard operating procedure, the raw materials are as follows: thioether II-f (14.81 mg, 0.071 mmol, 1.2 equivalents), benziodooxolane reagent Vf (13.40 mg, 0.018 mmol, 0.3 equivalents), receptor IV-29 (30.0 mg, 0.059 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-22 (34.3 mg, 98%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ8.00-7.97(m,2H),7.96-7.92(m,2H),7.90-7.85(m,2H),7.53-7.48(m,2H),7.44-7.40(m,1H),7.39-7.35 (m,4H),7.31-7.26(m,2H),6.17-6.11(m,1H),5.66(t,J=10.2Hz,0.57H),5.60(t,J=10.2Hz,0.43H),5.28(dt,J=3.6,10.2Hz,1H ),5.25(d,J=3.6Hz,1H),4.66(t,J=3.6Hz,0.57H),4.56(t,J=3.6Hz,0.43H),4.28-4.23(m,1H),3.98-3.94(m,1H),3.86-3.82( m,0.43H),3.71-3.66(m,0.57H),3.64-3.59(m,1H),3.48(s,3H),3.47-3.43(m,0.43H),3.39-3.34(m,0.57H),1.85-1.42(m,6H) 13 C NMR (150MHz, CDCl3) δ166.0, 165.4, 165.4, 133.5, 133.4, 133.2, 130.1, 1 29.9, 129.9, 129.8, 129.8, 129.5, 129.4, 129.3, 129.3, 128.5, 128.5, 128 .4,99.8,98.4,97.1,97.0,72.3,72.3,70.9,70.8,69.8,69.6,69.2,68.6 ,66.3,65.7,62.4,61.6,55.6,55.6,30.5,30.4,25.5,25.5,19.5,18.9..

[0230] Embodiment 76:

[0231]

[0232] According to the standard operating procedure, the raw materials are as follows: thioether II-f (15.42 mg, 0.074 mmol, 1.2 equivalents), benziodooxolane reagent Vf (13.95 mg, 0.018 mmol, 0.3 equivalents), receptor IV-19 (20.0 mg, 0.061 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-23 (23.9 mg, 95%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ7.42-7.38(m,0.64H),7.36-7.30(m,1.36H),7.29-7.19(m,3H),5.48(s,0.36H),5.43(s ,0.64H),4.95(t,J=3.2Hz,0.64H),4.84-4.78(m,2H),4.76(dd,J=4.0,9.6Hz,0.36H),4.21-4.10(m,2H),3.93 (td,J=2.8,11.2Hz,0.36H),3.83-3.71(m,1.64H),3.68-3.61(m,1H),3.57-3.50(m,1H),3.44-3.38(m,0.64H ),3.29(s,1.92H),3.28(s,1.08H),3.27-3.21(m,0.36H),2.04(s,1.92H),2.00(s,1.08H),1.66-1.30(m,6H). 13 C NMR (150MHz, CDCl3) δ170.8,170.6,170.4,137.5,137.4,137.1,129.5,129.1,129.0,128.5,128.4,12 8.2,126.4,126.2,126.1,102.2,101.5,101.4,98.5,98.5,98.0,97.8,97.7,94.8,94.5,82.7,81.6,80 .3,74.5,72.8,72.1,72.1,69.1,69.0,68.8,64.0,63.1,62.8,62.3,62.1,61.4,61.2,55.5,55.4,55.3,32.1,30.8,30.5,30.5,29.8,25.6,25.6,25.5,25.5,25.4,21.2,21.1,21.1,20.4,19.9,18.7,18.5.

[0233] Embodiment 77:

[0234]

[0235] According to the standard operating procedure of the reaction, the raw materials are as follows: thioether II-f (12.36 mg, 0.059 mmol, 1.2 equivalents), benziodooxolane reagent Vf (11.19 mg, 0.015 mmol, 0.3 equivalents), receptor IV-14 (20.0 mg, 0.049 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-24 (22.9 mg, 95%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ5.97 (d, J=9.6Hz, 1H), 5.76 (dd, J=6.0, 9.6Hz1H), 5.50 (t, J=3.6Hz, 1H),5.37-5.31(m,1H),4.66(dt,J=3.2,10.8Hz,1H),4.62-4.42(m,1H),4.26-4.18(m,1H) ,3.84-3.75(m,1H),3.54-3.45(m,1H),2.82-2.67(m,1H),2.67-2.52(m,1H),2.44-2.20(m ,4H),1.56-1.21(m,10H),1.08(d,J=6.8Hz,1H),1.05(d,J=7.6Hz,1H),0.89-0.82(m,6H). 13 C NMR (150MHz, CDCl3) δ176.72,176.69,170.46,170.21,133.25,133.22,131.82,131.77, 129.78,128.45,97.45,97.21,76.71,67.99,67.12,66.89,63.10,62.45,41.53,37.39,3 7.34,36.85,36.81,35.67,35.16,33.53,33.33,32.72,32.67,30.95,30.91,30.84,27.60,26.96,25.43,25.42,24.44,24.41,22.93,19.75,19.27,16.40,16.35,14.03,11.79.

[0236] Embodiment 78:

[0237]

[0238] According to the standard operating procedure, the raw materials are as follows: thioether II-f (16.54 mg, 0.079 mmol, 1.2 equivalents), benziodooxolane reagent Vf (14.96 mg, 0.020 mmol, 0.3 equivalents), receptor IV-28 (20.0 mg, 0.066 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-25 (25.0 mg, 98%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ5.71 (dd, J=2.0, 7.6Hz, 1H), 4.72-4.66 (m, 1H), 3.87 (ddd, J=3.6, 6.8, 14.4Hz, 1H), 3.62 ( m,1H),3.51-3.43(m,1H),2.79(m,1H),2.64-1.90(m,8H),1.86-1.46(m,11H),1.26-1.11(m,6H),0.86(s,3H). 13 CNMR (150MHz, CDCl3) δ220.5, 220.5, 201.2, 166.8, 166.5, 126.0, 126.0, 97.6, 97.3, 74.9, 74.7, 63.1, 63.1, 50.2, 48.0, 45.9, 44.5,40.3,39.0,38.8,38.8,36.6,36.3,35.8,31.3,31.2,30.9,29.5,27.8,25.5,24.3,20.7,20.7,20.0,20.0,17.5,13.9..

[0239] Embodiment 79:

[0240]

[0241] According to the standard operating procedure, the raw materials are as follows: thioether II-g (10.54 mg, 0.024 mmol, 1.2 equivalents), benziodooxolane reagent Vf (4.47 mg, 0.059 mmol, 0.3 equivalents), receptor IV-29 (10.0 mg, 0.020 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), and the target product VII-26 (17.1 mg, 96%) is obtained after the reaction is completed. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ7.97-7.93(m,2H,Ar-H),7.93-7.89(m,2H,Ar-H),7.86-7.82( m,2H,Ar-H),7.52-7.46(m,2H,Ar-H),7.42-7.38(m,1H,Ar-H),7.38-7.33(m,4H,Ar- H),7.29-7.25(m,2H,Ar-H),6.11(t,J=9.6Hz,1H,H-3),5.63(t,J=9.6Hz,1H,H-4), 5.25(dd,J=3.6,9.6Hz,1H,H-2),5.22(d,J=3.6Hz,1H,H-1),4.74(d,J=6.6Hz,1H,OC H2 O), 4.71(d, J=6.6Hz,1H,OC H2 O),4.19(dt,J=3.0,10.2Hz,1H,H-5),3.77-3.70(m,2H,H-6a,H-6b),3.68-3.48(m,32H),3.50(s,3H),3.35(s,3H). 13 C NMR (150MHz, CDCl3) δ166.0, 165.4, 133.5, 133.5, 133.2, 130.1, 129.9, 129.8, 129.4, 129.2, 129.2, 128.6,1 28.5,128.4,97.2,95.9,72.2,72.1,70.8,70.7,70.7,70.7,70.6,70.5,69.4,68.8,67.1,66.0,59.2,55.8.

[0242] Embodiment 80:

[0243]

[0244] According to the standard operating procedure, the raw materials are as follows: thioether II-g (17.65 mg, 0.040 mmol, 1.2 equivalents), benziodooxolane reagent Vf (7.49 mg, 0.099 mmol, 0.3 equivalents), receptor IV-28 (10.0 mg, 0.033 mmol, 1.0 equivalents), acid catalyst Tf2O (5 mol%), after the reaction is complete, the target product VII-27 (18.9 mg, 82%) is obtained by separation and purification by silica gel column chromatography. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ5.71 (d, J=1.6Hz, 1H), 4.82-4.71 (m, 2H), 3.72-3.65 (m, 2H), 3.65-3.49 (m, 32H), 3.35 (s, 3H), 2.84-2.74 (m, 1H), 2.57 (ddd, J=2.4,4.8,14.0Hz,1H),2.49-2.32(m,3H),2.17-2.05(m,1H),2.02-1.9 0(m,2H),1.87-1.68(m,6H),1.661.51(m,4H),1.19(s,3H),0.87(s,3H). 13 CNMR (150MHz, CDCl3) δ220.5, 201.1, 166.3, 126.1, 94.1, 75.6, 72.1, 70.8, 70.8, 70.7, 70.7, 70.6 ,67.2,59.2,50.2,48.0,45.9,44.5,39.6,38.7,36.4,35.8,30.9,28.6,24.3,20.7,17.5,13.9..

[0245] Embodiment 81:

[0246]

[0247] According to the standard operating procedure, diosgenin thiocarbonate III-1 (124.8 mg, 0.045 mmol, 1.5 equiv) and receptor IV-29 (15.2 mg, 0.03 mmol, 1.0 equiv), benzoiodine oxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalents of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 7 hours. The target product VIII-1 (25.0 mg, 92%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ8.007.89(m,4H),7.86-7.82(m,2H),7.52-7.47(m,2H),7.41-7.34(m,5H),7.26(t,J=7.8Hz,2H),6.11(t,J=9 .6Hz,1H),5.63(t,J=9.6Hz,1H),5.24(dt,J=10.2,3.6Hz,3H),4.39-4.35(m,1H),4.17-4.14(m,1H),3.73(dd,J=10.8,3.0Hz,1H),3 .59(dd,J=10.8,4.8Hz,1H),3.48-3.39(m,4H),3.35(t,J=10.8Hz,1H),3.10-3.02(m,1H),2.27-2.24(m,1H),2.19-2.11(m,1H),2.0 0-1.90(m,2H),1.89-1.35(m,18H),1.28-1.23(m,1H),1.15-1.10(m,1H),1.08-1.03(m,1H),1.00-0.85(m,8H),0.79-0.72(m,6H).

[0248] Embodiment 82:

[0249]

[0250] According to the standard operating procedure, diosgenin xanthate III-2 (22.7 mg, 0.045 mmol, 1.5 equiv) and receptor IV-29 (15.2 mg, 0.03 mmol, 1.0 equiv), benzoiodine oxalyl reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalents of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 12 hours. The target product (23.3 mg, 86%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ8.00-7.89(m,4H),7.86-7.82(m,2H),7.52-7.47(m,2H),7.41-7.34(m,5H),7.26(t,J=7.8Hz,2H),6.11(t,J=9 .6Hz,1H),5.63(t,J=9.6Hz,1H),5.24(dt,J=10.2,3.6Hz,3H),4.39-4.35(m,1H),4.17-4.14(m,1H),3.73(dd,J=10.8,3.0Hz,1H),3 .59(dd,J=10.8,4.8Hz,1H),3.48-3.39(m,4H),3.35(t,J=10.8Hz,1H),3.10-3.02(m,1H),2.27-2.24(m,1H),2.19-2.11(m,1H),2.0 0-1.90(m,2H),1.89-1.35(m,18H),1.28-1.23(m,1H),1.15-1.10(m,1H),1.08-1.03(m,1H),1.00-0.85(m,8H),0.79-0.72(m,6H).

[0251] Embodiment 83:

[0252]

[0253] According to the standard operating procedure, cholesterol xanthate III-3 (21.4 mg, 0.045 mmol, 1.5 equiv) and receptor IV-29 (15.2 mg, 0.03 mmol, 1.0 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalents of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 12 hours. The target product VIII-2 (27.3 mg, 84%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ7.95 (m, 4H), 7.85 (d, J=7.8Hz, 2H), 7.49 (m, 2H), 7.43-7.33 (m, 5H), 7.26 (t, J= 7.8Hz,2H),6.11(t,J=9.6Hz,1H),5.63(t,J=9.6Hz,1H),5.28-5.21(m,3H),4.20-4.14(m,1H),3.73 (dd,J=10.8,2.4Hz,1H),3.60(dd,J=10.8,4.8Hz,1H),3.46(s,3H),3.13-3.03(m,1H),2.25(dd,J=1 3.2, 2.4Hz, 1H), 2.15 (dd, J=18.0, 6.6Hz, 1H), 1.99-1.76 (m, 5H), 1.58-0.79 (m, 36H), 0.64 (s, 3H).

[0254] Embodiment 84:

[0255]

[0256] According to the standard operating procedure, cholesterol xanthate III-3 (21.4 mg, 0.045 mmol, 1.5 equiv) and receptor IV-30 (4.6 mg, 0.03 mmol, 1.0 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalent of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was continued at 0°C for 2 h. The target product VIII-3 (14.3 mg, 92%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ5.30-5.25(m,1H),3.47-3.41(m,1H),2.26(m,1H),2.13-2.05(m,4H),2.02-1.92(m,2H),1.81-0.85(m,50H),0.65(s,3H).

[0257] Embodiment 85:

[0258]

[0259] According to the standard operating procedure, cholesterol xanthate III-3 (21.4 mg, 0.045 mmol, 1.5 equiv) and receptor IV-31 (6.3 mg, 0.03 mmol, 1.0 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalent of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was continued at 0°C for 4 hours. The target product VIII-4 (16.9 mg, 97%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3)) δ5.35 (d, J=4.8Hz, 1H), 4.15 (dt, J=10.8, 4.8Hz, 1H), 4.00 (m, 4H), 2 .43-2.36(m,2H),2.01-1.92(m,3H),1.86-1.77(m,2H),1.67-0.83(m,48H),0.65(s,3H)..

[0260] Embodiment 86:

[0261]

[0262] According to the standard operating procedure, cholesterol xanthate III-3 (21.4 mg, 0.045 mmol, 1.5 equiv) and receptor IV-01 (13.9 mg, 0.03 mmol, 1.0 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalent of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 2 h. The target product VIII-5 (23.6 mg, 94%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1H NMR (400MHz, CDCl3) δ7.31-7.19(m,15H),5.16(d,J=4.8Hz,1H),4.87(d,J=10.4Hz, 1H),4.75-4.68(m,2H),4.58-4.49(m,3H),4.43(d,J=12.0Hz,1H),3.79(t,J=9.2Hz ,1H),3.64-3.56(m,3H),3.52-3.41(m,3H),3.31(s,3H),2.38-2.30(m,1H),2.14-2 .08(m,1H),1.95-1.86(m,2H),1.79-1.65(m,3H),1.47-0.79(m,34H),0.61(s,3H).

[0263] Embodiment 87:

[0264]

[0265] According to the standard operating procedure, cholesterol xanthate III-3 (14.3 mg, 0.03 mmol, 1.0 equiv) and receptor IV-31 (7.8 mg, 0.045 mmol, 1.5 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalents of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 6 hours. The target product VIII-6 (12.0 mg, 74%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1 H NMR (400MHz, CDCl3) δ7.37-7.25(m,2H),6.75(d,J=8.8Hz,2H),5.37(d,J=5.2Hz,1H),4.14-3.95(m,1 H),2.40(m,2H),2.06-1.93(m,3H),1.89(m,1H),1.85-1.75(m,1H),1.71-0.84(m,35H),0.66(s,3H).

[0266] Embodiment 88:

[0267] The reaction formula is as follows:

[0268]

[0269] According to the standard operating procedure, cholesterol xanthate III-3 (21.4 mg, 0.045 mmol, 1.5 equiv) and receptor IV-03 (7.8 mg, 0.03 mmol, 1.0 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalent of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 3 h. The target product VIII-7 (17.9 mg, 95%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ5.51 (d, J=4.8Hz, 1H), 5.41-5.27 (m, 1H), 4.57 (dd, J=7.8, 2.4Hz, 1H), 4.28-4.24 (m, 2H), 3.91-3.89 (m, 1H), 3.66-3.58(m,2H),3.21-3.16(m,1H),2.37-2.33(m,1H),2.22-2.15(m,1H),2.01-1.76(m,5H),1.63-0.83(m,48H),0.65(s,3H).

[0270] Embodiment 89:

[0271]

[0272] According to the standard operating procedure, cholesterol xanthate III-3 (14.3 mg, 0.045 mmol, 1.5 equiv) and receptor IV-32 (13.9 mg, 0.03 mmol, 1.0 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalent of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.0 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 6 hours. The target product VIII-8 (20.0 mg, 80%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1H NMR (600MHz, CDCl3) δ7.35-7.22(m,13H),7.16-7.10(m,2H),5.36-5.28(m,1H),4.83(d,J =10.8Hz,1H),4.70(dd,J=10.2,6.6Hz,2H),4.66-4.62(m,2H),4.53(d,J=12.0Hz,1H),4. 46(d,J=10.8Hz,1H),3.90-3.68(m,6H),3.37-3.28(m,4H),2.43-2.40(m,1H),2.35-2.26 (m,1H),2.04-1.92(m,2H),1.81(dd,J=9.8,4.2Hz,3H),1.66-0.80(m,37H),0.66(s,3H).

[0273] Embodiment 90:

[0274]

[0275] According to the standard operating procedure, 1.0 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalent of reactants) was added under argon, the reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 12 hours. The target product VIII-9 (24.1 mg, 89%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 1 H NMR (600MHz, CDCl3) δ8.00-7.90(m,4H),7.87-7.83(m,2H),7.52-7.47(m,2H),7.42-7.38(m,1H),7.38-7.33 (m,4H),7.29-7.25(m,2H),6.11(t,J=9.6Hz,1H),5.63(t,J=9.6Hz,1H),5.26-5.23(m,3H),4.17(ddd,J=10.8 ,4.8,3.0Hz,1H),3.73(dd,J=10.8,3.0Hz,1H),3.60(dd,J=10.8,4.8Hz,1H),3.46(s,3H),3.11-3.06(m,1H), 2.26-2.23(m,1H),2.20-2.11(m,1H),2.01-1.76(m,5H),1.66-1.61(m,1H),1.53-0.79(m,36H),0.64(s,3H).13 C NMR (150MHz, CDCl3) δ166.1,165.4,141.0,133.5,133.5,133.2,130.2,130.0,129.9,129 .6,129.5,129.4,128.6,128.5,121.8,97.2,80.5,72.4,70.9,69.9,69.2,67.1,57.0,56 .3,55.7,50.3,46.0,42.5,40.0,39.1,37.4,37.0,36.4,34.2,32.1,32.1,29.4,28.5,28 .3,26.3,24.5,23.3,21.3,20.0,19.6,19.2,19.0,12.2,12.1.HRMS(ESI-TOF)m / z:[M+Na] + calc.for C 57 H 74 O9Na 925.5225,found:925.5219.

[0276] Embodiment 91:

[0277]

[0278] According to the standard operating procedure, stigmasterol xanthate III-4 (22.7 mg, 0.045 mmol, 1.5 equiv) and receptor IV-29 (15.2 mg, 0.03 mmol, 1.0 equiv), benziodooxolane reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalents of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 12 hours. The target product VIII-10 (21.8 mg, 80%) was obtained by purification by silica gel column chromatography. The characterization data of the compound are as follows: 11H NMR (600 MHz, CDCl3) δ 7.99 - 7.86 (m, 4H), 7.87 - 7.81 (m, 2H), 7.50 - 7.47 (m, 2H), 7.41 - 7.38 (m, 1H), 7.37 - 7.34 (m, 4H), 7.27 - 7.25 (m, 2H), 6.11 (t, J = 9.6 Hz, 1H), 5.63 (t, J = 9.6 Hz, 1H), 5.26 - 5.23 (m, 3H), 5.13 (dd, J = 15.0, 9.0 Hz, 1H), 4.99 (dd, J = 15.0, 9.0 Hz, 1H), 4.17 (ddd, J = 10.8, 4.8, 3.0 Hz, 1H), 3.73 (dd, J = 10.8, 3.0 Hz, 1H), 3.60 (dd, J = 10.8, 4.8 Hz, 1H), 3.46 (s, 3H), 3.16 - 3.03 (m, 1H), 2.24 - 2.23 (m, 1H), 2.18 - 2.11 (m, 1H), 2.04 - 1.88 (m, 3H), 1.87 - 1.82 (m, 1H), 1.78 (dt, J = 13.2, 3.0 Hz, 1H), 1.71 - 1.63 (m, 1H), 1.54 - 1.37 (m, 9H), 1.24 - 0.77 (m, 22H), 0.66 (s, 3H). 13 13C NMR (150 MHz, CDCl3) δ 166.1, 165.4, 141.0, 138.5, 133.5, 133.5, 133.2, 130.2, 130.0, 129.9, 129.6, 129.5, 129.5, 129.4, 128.6, 128.5, 121.8, 97.2, 80.5, 72.4, 70.9, 69.8, 69.2, 67.1, 57.1, 56.2, 55.7, 51.4, 50.4, 42.4, 40.7, 39.9, 39.1, 37.4, 37.1, 32.1, 32.1, 32.1, 29.1, 28.2, 25.6, 24.6, 21.4, 21.3, 21.2, 19.6, 19.2, 12.5, 12.2. HRMS (ESI-TOF) m / z: [M+Na] + calc. for C 57 H 72 O9Na923.5069, found: 923.5071.

[0279] Example 92:

[0280]

[0281] According to the standard operating procedure of the reaction, pregnenolone xanthate III-6 (18.3 mg, 0.045 mmol, 1.5 equiv) and receptor IV-29 (15.2 mg, 0.03 mmol, 1.0 equiv), benzoiodine oxaline reagent Vf (9.0 mg, 0.012 mmol, 0.4 equiv) and pre-activated molecular sieves were added to the reaction bottle, and anhydrous DCM (c = 0.1 M, calculated based on 1.0 equivalents of reactants) was added under argon. The reaction system was precooled to 0°C, TMSOTf (2.2 μL, 0.012 mmol, 0.4 equiv) was added, and the reaction was carried out at 0°C for 24 hours. The target product VIII-11 (16.5 mg, 69%) was obtained by purification by silica gel column chromatography. 1 H NMR (600MHz, CDCl3) δ7.96-7.92(m,4H),7.85(d,J=7.8Hz,2H),7.51-7.47(m,2H),7.44-7.31(m,5H),7.26(t,J=7.8Hz,2 H),6.11(t,J=9.6Hz,1H),5.63(t,J=9.6Hz,1H),5.26-5.23(m,3H),4.21-4.10(m,1H),3.73(dd,J=10.8,2.4Hz,1H),3.60 (dd,J=10.8,4.8Hz,1H),3.46(s,3H),3.16-3.05(m,1H),2.49(t,J=9.0Hz,1H),2.28-2.24(m,1H),2.19-2.12(m,2H),2. 09(s,3H),2.02-1.178(m,4H),1.68-1.59(m,3H),1.58-1.36(m,6H),1.28-1.03(m,3H),1.00-0.89(m,5H),0.60(s,3H).

[0282] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A glycosidation method involving a benziodooxolane reagent, characterized in that: The method specifically comprises: activating the glycosyl donor as shown in formula I under the joint action of a benziodooxolane reagent as shown in formula V and an acid catalyst, and then reacting with a nucleophilic reagent to obtain a glycosylation product as shown in formula VI. The reaction route is as shown in formula 1: Formula 1: In the glycosyl donor as shown in Formula I, one or more hydroxyl groups on the sugar ring are protected by a glycosyl protecting group, and LG is an alkylthio group, an arylthio group, an aryl selenoyl group, a thiocarboxylate group, an o-alkynyl benzoate group, a pentenoate group, a pentynoate group or a hexynoate group; In the benzoiodine oxolane reagent shown in Formula V, R 1 is chlorine, hydroxyl, trimethylsilyloxy, trifluoromethanesulfonyl ester or benzoiodine oxolane oxy, R 2 is methyl or trifluoromethyl; Nu in the formula 1 represents a nucleophile, and the nucleophile is selected from primary alcohol, secondary alcohol or carboxylic acid.

2. The glycosidation method involving the benziodooxolane reagent as claimed in claim 1, characterized in that: The glycosyl donor as shown in Formula I is selected from the following compounds of any structure:

3. The glycosidation method involving the benziodooxolane reagent as claimed in claim 1, characterized in that: The benzoiodine oxolane reagent shown in Formula V is selected from compounds of any of the following structures:

4. The glycosidation method involving the benziodooxolane reagent as claimed in claim 1, characterized in that: The molar ratio of the glycosyl donor to the benziodonium oxolane reagent is 1:(0.25-0.5).

5. The glycosidation method involving the benziodooxolane reagent as claimed in claim 1, characterized in that: The nucleophilic agent is selected from the following compounds:

6. An alkylation method involving a benziodooxolane reagent, characterized in that: The method specifically comprises: activating an alkylating agent as shown in formula II under the joint action of a benziodooxolane reagent as shown in formula V and an acid catalyst, and then reacting with a nucleophilic agent to obtain an alkylated product as shown in formula VII. The reaction route is as shown in formula II; Alternatively, the alkylating agent shown in Formula III is activated under the combined action of a benziodooxolane reagent shown in Formula V and an acid catalyst, and then reacts with a nucleophilic reagent to obtain an alkylated product shown in Formula VIII. The reaction route is shown in Formula III; Formula 2: Formula 3: The alkylating agent shown in Formula II is a thioether alkylating agent, wherein R 3 is an alkyl group, R 4 is an alkyl group or an aryl group; The alkylating agent shown in Formula III is a steroidal derivative containing a homoallyl thiocarbonate structure, wherein the steroid is cholesterol, dioscin, dehydroepiandrosterone, pregnenolone, β-sitosterol, stigmasterol; wherein R 5 is phenoxy or methylthio; In the benzoiodine oxolane reagent shown in Formula V, R 1 is chlorine, hydroxyl, trimethylsilyloxy, trifluoromethanesulfonyl ester or benzoiodine oxolane oxy, R 2 is methyl or trifluoromethyl; Nu in Formula 2 and Formula 3 both represent nucleophiles, and the nucleophiles are selected from primary alcohols, secondary alcohols, phenols or phosphoric acids.

7. The alkylation method involving a benziodooxolane reagent as claimed in claim 6, characterized in that: The alkylating agent as shown in Formula II is selected from compounds of any of the following structures: The alkylating agent as shown in formula III is selected from compounds of any of the following structures:

8. The alkylation method involving a benziodooxolane reagent as claimed in claim 6, characterized in that: The benzoiodine oxolane reagent shown in Formula V is selected from compounds of any of the following structures:

9. The alkylation method involving a benziodooxolane reagent as claimed in claim 6, characterized in that: The molar ratio of the alkylating agent shown in formula II to the benzoiodine oxolane reagent is 1:(0.25-0.5); the molar ratio of the alkylating agent shown in formula III to the benzoiodine oxolane reagent is 1:(0.25-0.5).

10. The alkylation method involving a benziodooxolane reagent as claimed in claim 6, characterized in that: The nucleophilic agent is selected from the following compounds:

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