A type ii lipoteichoic acid and a method for preparing the same

Abstract

The application belongs to the technical field of biological medicine and chemical synthesis, and particularly relates to a type II lipoteichoic acid and a preparation method thereof. The type II lipoteichoic acid is selected from a compound shown in the following formula I, wherein X is independently selected from H or a fatty acyl group. The application adopts a pre-activated O-glycosyl trichloroacetimidate donor glycosylation method to sequentially construct different types of alpha-configuration glycoside bonds in the molecule, and prepares a lipoteichoic acid skeleton unit through coupling of phosphate esters. The method has the advantages of high conversion rate, low cost, large-scale preparation and the like, and therefore has good practical application value.

Description

Technical Field

[0001] This invention belongs to the fields of biomedicine and chemical synthesis technology, specifically relating to a type II lipoteichoic acid and its preparation method. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Carbohydrates, as one of the fundamental substances of life, play a vital role in life activities. Given their value in biological activity research and pharmaceutical applications, the synthesis of carbohydrates with uniform and well-defined structures is of paramount importance.

[0004] Lipoteichoic acid (LTA) is an important component of the cell wall of Gram-positive bacteria. Its main skeletal structure consists of hydrophilic glycerol (with a small portion of ribitol) phosphodiester bonds. The hydroxyl groups at non-linking sites on the backbone have varying numbers and types of substituents (e.g., D-alanine or various sugars). The ends of the backbone are attached to lipophilic glycolipid structures, anchored to the cell membrane via long fatty chains. As important pathogen-associated molecular patterns (PAMPs) on the bacterial surface, LTA can bind to specific pattern recognition receptors (PRPs) on immune cells, activating the innate immune system to resist bacterial invasion. Efficient and large-scale preparation of LTA molecules will facilitate in-depth research on its immunostimulatory effects and explore its medicinal applications.

[0005] Due to the complex structure of lipoteichoic acid, its synthesis remains challenging. Currently, synthetic methods for type I, IV, and V lipoteichoic acids have been established, but the synthesis of type II lipoteichoic acid has not yet been reported. The structure of type II lipoteichoic acid includes sugar chains, fat granules, sugar alcohols, and a phosphate ester backbone, and contains five different types of 1,2-cis glycosidic bonds, which is a major challenge in the synthesis of this class of molecules. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a type II lipoteichoic acid and its preparation method. The synthetic route of this invention is simple and efficient, the operation is simple and safe, it is highly practical, and it is easy to scale up for production.

[0007] Specifically, the technical solution of the present invention is as follows:

[0008] In a first aspect, the present invention provides a compound selected from compounds of Formula I.

[0009]

[0010] Wherein, X is independently selected from: H or fatty acyl group;

[0011] The fatty acyl group can be a saturated fatty acyl group or an unsaturated fatty acyl group. In one specific embodiment of the present invention, the fatty acyl group is -COC. 13 H 27

[0012] The compound also includes its pharmaceutically acceptable salts or esters or solvates, tautomers, mesosomes, racemates, stereoisomers or metabolites.

[0013] A second aspect of the present invention provides a method for preparing the above-mentioned compound, wherein the synthetic route of the compound represented by Formula I includes:

[0014]

[0015] A third aspect of the present invention provides a composition comprising at least the compounds described above.

[0016] The beneficial effects of one or more of the above technical solutions:

[0017] The above technical solution provides a type II lipoteichoic acid and its preparation method. Specifically, the solution employs a glycosylation method based on a pre-activated O-glycosyltrichloroacetilime ester donor to sequentially construct different types of α-glycosidic bonds in the molecule; and prepares the lipoteichoic acid skeleton unit through phosphate ester coupling. This preparation method has advantages such as high conversion rate, low cost, and large-scale production capability. The obtained type II lipoteichoic acid compound can be used as an important component of the cell wall of Lactococcus gasseri and its structural analogues, thus having promising practical application prospects in fields such as medicine. Attached Figure Description

[0018] The accompanying drawings, which form part of this invention, are used to provide a further understanding of this application. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0019] Figure 1 NMR spectrum of compound 1-1;

[0020] Figure 2 NMR spectra of compounds 1-2;

[0021] Figure 3NMR spectrum of compound 3-1;

[0022] Figure 4 NMR spectrum of compound 3-2;

[0023] Figure 5 NMR spectrum of compound 4-1;

[0024] Figure 6 NMR spectrum of compound 5-1;

[0025] Figure 7 NMR spectrum of compound 5-2;

[0026] Figure 8 NMR spectrum of compound 5-3;

[0027] Figure 9 NMR spectrum of compound 5-4. Detailed Implementation

[0028] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0029] To enable those skilled in the art to better understand the technical solution of the present invention, the following detailed description will be provided in conjunction with specific embodiments.

[0030] In a typical embodiment of the present invention, a compound is provided, which is selected from compounds represented by Formula I.

[0031]

[0032] Wherein, X is independently selected from: H or fatty acyl; n is taken from 1 to 50, and further n is taken from 16 to 40;

[0033] The fatty acyl group can be a saturated fatty acyl group or an unsaturated fatty acyl group. In one specific embodiment of the present invention, the fatty acyl group is -COC. 13 H 27

[0034] The compound also includes its pharmaceutically acceptable salts or esters or solvates, tautomers, mesosomes, racemates, stereoisomers or metabolites.

[0035] In another specific embodiment of the present invention, a method for preparing the above-mentioned compound is provided, wherein the synthetic route of the compound represented by Formula I includes:

[0036]

[0037] Specifically, the preparation method includes:

[0038] S1. Compound 1 and N,N-diisopropylammonium tetrazolium salt were reacted at room temperature for a period of time, and then 2-cyanoethyl N,N,N,N-tetraisopropylphosphine diamine was added and the reaction was continued until complete. The mixture was filtered and concentrated to obtain a semi-solid product 2, which was used directly in the next step of synthesis without purification.

[0039] S2. Compound 2 and compound 3 were reacted under tetrazolium conditions until the starting material was completely eliminated. The reaction system was placed in an ice-water bath, peroxytert-butanol was added and the mixture was stirred until the reaction was complete. Compound 4 was obtained by purification.

[0040] S3. Compound 5 is obtained by removing the protecting group from compound 4.

[0041] Wherein, compound 1 can be compound 1-1 or compound 1-2; compound 3 can be compound 3-1 or compound 3-2;

[0042]

[0043] The compound 4 can be compound 4-1, compound 4-2, compound 4-3 or compound 4-4, and the compound 5 can be compound 5-1, compound 5-2, compound 5-3 or compound 5-4.

[0044]

[0045] It should be noted that in the structural formulas of the above compounds, Bn represents benzyl.

[0046] Furthermore, compound 1 was prepared using a glycosylation method based on a pre-activated O-glycosyltrichloroacetimide ester donor.

[0047] When compound 1 is compound 1-1, its synthetic route is as follows:

[0048]

[0049] Specifically, the steps include: (1) Compound 6 and Compound 7 are glycosylated using a pre-activated O-glycosyl trichloroacetylimine ester donor glycosylation method to prepare Compound 8; (2) Compound 8 is deprotected by an allyl group to obtain Compound 9-1, which is then glycosylated with Compound 10 using a pre-activated O-glycosyl trichloroacetylimine ester donor glycosylation method to prepare Compound 11-1; (3) Compound 11-1 is deprotected by a TBDPS protecting group to obtain Compound 12-1, which is then glycosylated with Compound 7 using a pre-activated O-glycosyl trichloroacetylimine ester donor glycosylation method to prepare Compound 13-1; (4) Compound 13-1 is deprotected by a Bz protecting group to obtain Compound 1-1.

[0050] Furthermore, when compound 1 is compound 1-2, its synthetic route is as follows:

[0051]

[0052] Specifically, the steps include: (1) Compound 6 and Compound 7 are glycosylated using a pre-activated O-glycosyl trichloroacetilime ester donor glycosylation method to prepare Compound 8; (2) Compound 8 is deprotected by the Bz protecting group to obtain Compound 9-2, and then Compound 9-2 is prepared by glycosylation using a pre-activated O-glycosyl trichloroacetilime ester donor glycosylation method with Compound 10; (3) Compound 11-2 is deprotected by the TBDPS protecting group to obtain Compound 12-2, and then Compound 12-2 is prepared by glycosylation using a pre-activated O-glycosyl trichloroacetilime ester donor glycosylation method with Compound 7; (4) Compound 13-2 is deally removed to obtain Compound 1-2.

[0053] Furthermore, compound 3 was prepared using a glycosylation method based on a pre-activated O-glycosyltrichloroacetimide ester donor.

[0054] When compound 3 is compound 3-1, its synthetic route is as follows:

[0055]

[0056] Specifically, the steps include: (1) Compound 14 and Compound 15 are glycosylated using a pre-activated O-glycosyl trichloroacetylimine ester donor to prepare Compound 16; (2) Compound 16 is deprotected and myristylated to obtain Compound 17, which is then glycosylated with Compound 19 using a pre-activated O-glycosyl trichloroacetylimine ester donor to prepare Compound 20; (3) Compound 20 is deprotected by the Lev protecting group and myristylated to obtain Compound 21; (4) Compound 21 is deprotected by the TBDPS protecting group to obtain Compound 3-1.

[0057] When compound 3 is compound 3-2, its synthetic route is as follows:

[0058]

[0059] Specifically, the steps include: (1) Compound 14 and Compound 22 are glycosylated using a pre-activated O-glycosyl trichloroacetylimine ester donor to prepare Compound 23; (2) Compound 23 is deprotected and myristylated to obtain Compound 24, which is then glycosylated with Compound 19 using a pre-activated O-glycosyl trichloroacetylimine ester donor to prepare Compound 25; (3) Compound 25 is deprotected using a TBDPS protecting group to obtain Compound 3-2.

[0060] In another specific embodiment of the present invention, a composition is provided, the composition comprising at least the above-described compounds.

[0061] The following examples further illustrate the present invention, but do not constitute a limitation thereof. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the invention. Wherein, Bn is benzyl, All is allyl, Bz is benzoyl, TBDPS is tert-butyldiphenylsilyl, Lev is acetylacetyl, and PMB is p-methoxybenzyl.

[0062] Example

[0063] 1. Preparation of compound 1-1:

[0064]

[0065] Add to reaction flask Molecular sieves were used. The mixture was vacuum-sealed in a flask, cooled to room temperature, and then purged with argon gas. Glycosyl donor 7 (14.0 g, 20.0 mmol), dried DCM (245 mL), and DMF (23.7 mL, 307 mmol) were added, and the mixture was stirred at room temperature for 20 minutes. The reaction mixture was then cooled to -78°C, and TfOH (1.8 mL, 20.0 mmol) was added. Subsequent TLC analysis showed that the glycosyl donor had completely disappeared and a new spot had appeared. TBAI (37.7 g, 102 mmol) was then added, and TLC analysis showed that the second activation step was complete. The reaction mixture was placed in an ice-water bath, and glycosyl acceptor 6 (3.86 g, 16.4 mmol) was added. The temperature was gradually raised to room temperature, and the reaction was allowed to proceed for 48 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with triethylamine and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3 (aq.), Na2S2O3 (aq.), and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless oily substance 8 (10.0 g, 80%).1H NMR(400MHz,CDCl3)δ=8.03(d,J=7.7Hz,2H,ArH),7.51(t,J=7.4Hz,1H,ArH),7.42–7.14(m,22H,ArH),5.86(ddt,J=16.3,10.8,5.5Hz,1H,CH2CH=CH2),5.25(dd,J=17.2,1.8Hz,1H,CH2CH=CH2),5.20(d,J=3.7Hz,1H,1-H),5.15(d,J=10.5Hz,1H,CH2CH=CH2),4.90(d,J=11.4Hz,1H,PhCH2),4.81(d,J=12.0Hz,1H,PhCH2),4.78(d,J=12.0Hz,1H,PhCH2),4.71(d,J=11.8Hz,1H,PhCH2),4.70(d,J=11.6Hz,1H,PhCH2),4.55–4.49(m,2H,PhCH2,1”-H),4.43(dd,J=11.7,6.1Hz,1H,1”-H),4.32(d,J=11.8Hz,1H,PhCH2),4.25(d,J=11.8Hz,1H,PhCH2),4.22–4.17(m,1H,2”-H),4.14(t,J=6.8Hz,1H,5-H),4.06(dd,J=9.5,3.6Hz,1H,2-H),4.02–3.90(m,4H,CH2CH=CH2 X 2,3-H,4-H),3.69–3.59(m,2H,3”-H X 2),3.50(t,J=8.3Hz,1H,6-H),3.40(dd,J=9.0,5.8Hz,1H,6’-H).13C NMR(100MHz,CDCl3)δ=166.16,138.73,138.58,138.57,137.90,134.34,132.83,129.92,129.52,128.25,128.17,128.14,128.03,127.99,127.70,127.49,127.41,127.34,127.27,116.97,97.12,78.69,76.15,74.85,74.67,74.03,73.19,72.89,72.84,72.22,69.55,69.35,68.51,64.96.HRMS(ESI)Calcd for C47H54NO9[M+NH4]+:776.3793,found:776.3804.。

[0066] Compound 8 was dissolved in a mixed solution of DCM and MeOH (10 / 1, 100 mL), followed by the addition of PdCl2 (500 mg, 2.8 mmol). The mixture was stirred at room temperature for 8 hours until the reaction was complete. The precipitate was removed by filtration through diatomaceous earth. The filtrate was washed successively with saturated NaHCO3 and saturated brine, dried over anhydrous NaSO4, filtered, and concentrated. Purification by silica gel column chromatography yielded a colorless oily compound 9 (9.8 g, 97%). 11H NMR (400 MHz, CDCl3) δ 8.05–8.01 (m, 2H, ArH), 7.57–7.50 (m, 1H, ArH), 7.45–7.15 (m, 21H, ArH), 5.01 (d, J = 3.7 Hz, 1H, 1-H), 4.90 (d, J = 11.2, 1H, PhCH2), 4.89 (d, J = 11.2 Hz, 1H, PhCH2), 4.75 (s, 2H, PhCH2 X 2), 4.71 (d, J = 11.5 Hz, 1H, PhCH2), 4.53 (d, J = 11.3 Hz, 1H, PhCH2), 4.41 (dd, J = 11.7, 6.2 Hz, 1H, 1”-H), 4.36–4.32 (m, 1H, CH2-glycerol), 4.30 (d, J = 12.0 Hz, 1H, PhCH2), 4.23 (d, J = 11.7 Hz, 1H, PhCH2), 4.14–4.06 (m, 2H, 2-H, 5-H), 4.05–3.97 (m, 3H, 3-H, 4-H, 2”-H), 3.77–3.70 (m, 1H, 6-H), 3.66 (dd, J = 11.8, 7.4 Hz, 1H, 6’-H), 3.49 (t, J = 8.4 Hz, 1H, 3”-H), 3.31 (dd, J = 8.9, 5.5 Hz, 1H, 3”-H). 13C NMR (100 MHz, CDCl3) δ = 166.22, 138.55, 138.41, 137.82, 137.68, 133.05, 129.80, 129.66, 128.48, 128.37, 128.36, 128.29, 128.17, 128.03, 128.01, 127.69, 127.62, 127.54, 127.52, 127.35, 99.74, 79.45, 79.38, 76.15, 74.80, 74.50, 74.44, 73.30, 72.50, 69.75, 68.31, 64.48, 62.29. HRMS (ESI) Calcd for C44H50NO9 [M+NH4]+: 736.3480, found: 736.3490. HRMS Calcd for C44H46KO9 [M+K]+: 757.2773, found: 757.2770.

[0067] Add to the reaction flask Molecular sieves were used. The mixture was vacuum-sealed in a flask, cooled to room temperature, and then purged with argon gas. Glycosyl donor 10 (17.8 g, 21.4 mmol), dried DCM (270 mL), and DMF (24.8 mL, 321.0 mmol) were added, and the mixture was stirred at room temperature for 20 minutes. The reaction mixture was then cooled to -78°C, and TfOH (1.9 mL, 21.9 mmol) was added. Subsequent TLC analysis showed that the glycosyl donor had completely disappeared and a new spot had appeared. TBAI (39.5 g, 107.0 mmol) was then added, and TLC analysis showed that the second activation step was complete. The reaction mixture was placed in an ice-water bath, and glycosyl acceptor 11 (12.3 g, 17.1 mmol) was added. The temperature was gradually raised to room temperature, and the reaction was allowed to proceed for 48 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with triethylamine and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3 (aq), Na2S2O3 (aq.) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless oil 11 (20.7 g, 87%, α / β = 11.5 / 1). For αisomer: 1H NMR (500 MHz, CDCl3) δ = 7.97–7.91 (m, 2H, ArH), 7.55–7.48 (m, 4H, ArH), 7.42–7.3 (m, 1H, ArH), 7.32–7.06 (m, 40H, ArH), 5.11 (d, J = 3.6 Hz, 1H, 1a-H), 4.84 (d, J = 11.0 Hz, 1H, PhCH2). ,4.82(d,J=11.0Hz,1H,PhCH2),4.71(d,J=3.6Hz,1H,1b-H),4.70(d,J=12.0Hz,1H,PhCH 2),4.68(d,J=11.5Hz,1H,PhCH2),4.65(d,J=12.0Hz,1H,PhCH2),4.60–4.56(m,3H,PhCH2 X 3),4.52(d,J=12.0Hz,1H,PhCH2),4.50(d,J=12.0Hz,1H,PhCH2),4.46(d,J=11.5Hz ,1H,PhCH2),4.43(d,J=11.5Hz,1H,PhCH2),4.44–4.41(m,1H,1”-H),4.32(dd,J=11. 7,6.4Hz,1H,1”-H),4.25(d,J=11.8Hz,1H,PhCH2),4.18(d,J=11.9Hz,1H,PhCH2),4. 16–4.11(m,1H,2”-H),4.09–4.06(m,1H,5a-H),3.94(dd,J=9.5,3.5Hz,1H,2a-H),3.91(dd,J=10.0,3.5Hz,1H,2b-H),3.88–3.83(m,3H,3a-H,4a-H,4b-H)3.81(dd,J=10.1,2.8Hz,1H,3b-H),3.70–3.66(m,1H,5b-H),3 .66–3.61(m,3H,6b,6b'-H,3”-H),3.50–3.43(m,2H,3”-H,6a’-H),3.34(dd,J=8.9,5.6Hz,1H,6a’-H)0.95(s,9H,tert-Butyl).13C NMR (125MHz, CDCl3) δ=166.26,138.89,138.87,138.78,138.73,138.66,138.10,135.52,133.38,133.26,132.85,13 0.14,129.74,129.69,129.66,128.35,128.30,128.26,128.23,128.11,128.07,127.98,127.72,127.68,127.64,127 .52,127.48,127.45,127.41,127.39,127.36,127.32,98.33,96.88,79.10,78.81,76.49,76.39,75.23,75.12,74.83 ,74.78,73.58,73.35,73.13,73.09,72.89,71.28,69.55,68.64,67.23,65.26,62.73,26.92,19.15.HRMS(ESI)Calcd for C87H96NO14Si[M+NH4]+:1406.6595,found:1406.6597.

[0068] Preparation of the TBAF / AcOH mixture: Acetic acid was added dropwise to a TBAF THF solution (5 mL, 1 M in THF) until the pH of the mixture reached 6. Compound 11 (1.1 g, 0.79 mmol, in 2 mL of THF) was dissolved in THF (2 mL) and added to the above TBAF / AcOH mixture. The mixture was stirred at room temperature for 3 hours until the reaction was complete. The reaction was quenched with saturated NH4Cl and diluted with 50 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NH4Cl(aq) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a semi-solid compound 12 (730 mg, 80%). 1H NMR(500MHz,CDCl3)δ=7.99–7.90(m,2H,ArH),7.47–7.39(m,1H,ArH),7.33–7.07(m,38H,ArH),5.06(d,J=3.7Hz,1H,1a-H),4.84(d,J=12.0Hz,1H,PhCH2),4.82(d,J=12.0Hz,1H,PhCH2),4.75(d,J=3.5Hz,1H,1b-H),4.73(d,J=11.5Hz,1H,PhCH2),4.71(d,J=12.0Hz,1H,PhCH2),4.68(d,J=12.4Hz,1H,PhCH2),4.67(d,J=12.4Hz,1H,PhCH2),4.62(d,J=11.5Hz,1H,PhCH2),4.59(d,J=11.5Hz,1H,PhCH2),4.56(d,J=12.0Hz,1H,PhCH2),4.54(d,J=11.5Hz,1H,PhCH2),4.50(d,J=11.5Hz,1H),4.46–4.42(m,3H,PhCH2,3”-H X 2),4.26(d,J=11.9Hz,1H,PhCH2,),4.19(d,J=11.8Hz,1H,PhCH2,),4.16–4.08(m,1H,2”-H),4.04(t,J=6.7Hz,1H,5a-H),3.96(dd,J=10.0,4.0Hz,1H,2a-H),3.95(dd,J=10.5,3.5Hz,1H,2b-H),3.88–3.82(m,2H,4a-H,3a-H),3.80(dd,J=10.1,2.9Hz,1H,3b-H),3.76(dd,J=10.6,6.3Hz,1H,3”-H),3.70(d,J=2.8Hz,1H,4b-H),3.64(t,J=5.8Hz,1H,5b-H),3.55(dd,J=10.5,6.0Hz,1H,3”-H),3.57–3.49(m,1H,6b-H),3.42(t,J=8.5Hz,1H,6a-H),3.34(dd,J=9.4,5.8Hz,1H,6a’-H),3.37–3.29(m,1H,6b’-H),1.85(bs,1H,OH).13C NMR(125MHz,CDCl3)δ=66.38,138.80,138.75,138.68,138.32,138.04,133.03,130.07,129.68,128.45,128.40,128.35,128.31,128.19,128.15,127.85,127.79,127.72,127.69,127.63,127.60,127.58,127.55,127.51,127.47,127.44,98.43,97.39,78.96,78.86,76.62, 76.40,75.32,75.09,74.85,74.58,74.11,73.41,73.39,73.18,73.05,71.05,69.70,68.75,67.25,64.74,62.37.HRMS(ESI)Calcd for C71H78NO14[M+NH4]+:1168.5417,found:1168.5430.

[0069] Add to reaction flask Molecular sieves were used. The mixture was vacuum-sealed in a flask, cooled to room temperature, and then purged with argon gas. Glycosyl donor 7 (6.0 g, 8.8 mmol), dried DCM (270 mL), and DMF (10.2 mL, 132.0 mmol) were added, and the mixture was stirred at room temperature for 20 minutes. The reaction mixture was then cooled to -78°C, and TfOH (0.7 mL, 8.8 mmol) was added. Subsequent TLC analysis showed that the glycosyl donor had completely disappeared and a new spot had appeared. TBAI (16.2 g, 43.9 mmol) was then added, and TLC analysis showed that the second activation step was complete. The reaction mixture was placed in an ice-water bath, and glycosyl acceptor 12 (8.1 g, 7.0 mmol) was added. The temperature was gradually raised to room temperature, and the reaction was allowed to proceed for 48 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with triethylamine and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3 (aq), Na2S2O3 (aq.) and brine, dried over Na2SO4, filtered and concentrated. The residue was purified by silica gel column chromatography to give a colorless oil 13 (10.3 g, 89%, α / β = 16.8 / 1).

[0070] Compound 13 was dissolved in a DCM / MeOH (1 / 1) mixture, and NaOMe (1 M in MeOH) was added to adjust the pH to 9. The mixture was stirred at room temperature for 3 hours until the reaction was complete, and then H₂ was added. + The pH was adjusted to 7 using resin. The resin was filtered off, the filtrate was concentrated, and the residue was purified by silica gel column chromatography to obtain a colorless oil 1 (4.6 g, 87%). 1H NMR(600MHz,CDCl3)δ7.28–7.08(m,56H,ArH),5.02(d,J=3.7Hz,1H,1a-H),4.813(d,J=11.4,1H,PhCH2),4.808(d,J=11.4,1H,PhCH2),4.77(d,J=11.4Hz,1H,PhCH2),4.72(d,J=11.4Hz,1H,PhCH2),4.708(d,J=3.6Hz,2H,1b-H,1c-H),4.709(d,J=11.4Hz,1H,PhCH2),4.70(d,J=11.4Hz,1H,PhCH2),4.652(d,J=11.4Hz,1H,PhCH2),4.650(d,J=12.0Hz,1H,PhCH2),4.62(d,J=11.6Hz,1H,PhCH2),4.58(d,J=12.0Hz,1H,PhCH2),4.57–4.50(m,5H,PhCH2 X 5),4.46–4.40(m,3H,PhCH2 X3),4.39(d,J=11.6Hz,1H,PhCH2),4.37(d,J=12.0Hz,1H,PhCH2),4.28(d,J=11.8Hz,2H,PhCH2 X2),4.00(t,J=6.3Hz,1H,5a-H),3.96–3.89(m,4H,2a-H,2b-H,2c-H,3b-H),3.89–3.83(m,3H,2”-H,3a-H,3c-H),3.82–3.76(m,3H,5b-H,5c-H,3b-H),3.73(d,J=2.8Hz,1H,4c-H),3.73–3.68(m,3H,4a-H,6b-H,6c-H),3.65(dd,J=9.7,6.2Hz,1H,3”-H),3.55(dd,J=12.2,5.0Hz,1H,6b’-H),3.49(dd,J=10.2,5.4Hz,1H,6c’-H),3.47(dd,J=9.6,7.2Hz,1H,1”-H),3.44–3.40(m,2H,6a-H,1”-H),3.32(dd,J=9.7,6.6Hz,1H,3”-H),3.27(dd,J=9.4,5.4Hz,1H,6a’-H). 13C NMR (150MHz, CDCl3) δ = 138.74, 138.70, 138.65, 138.52, 138.49, 137.89, 137.65, 128.37, 128.34, 128.29, 128.26, 128.2 1,128.16,128.15,128.06,127.93,127.85,127.83,127.71,127.64,127.56,127.54,127.47,127.41,127.36,127.34,98 .26,98.10,97.24,79.27,78.94,78.86,78.08,76.46,76.29,76.22,75.03,74.96,74.82,74.74,74.59,74.58,73.58,73 .45,73.38,73.36,73.08,73.07,72.92,72.78,69.82,69.41,69.40,69.29,68.70,67.29,67.05,63.06.HRMS(ESI)Calcd for C 98 H 104 NaO 18 [M+Na] + :1592.7148,found 1592.7168.

[0071] 2. Preparation of compound 3-1

[0072]

[0073] Add to reaction flask Molecular sieves were used. A vacuum flask was prepared and cooled to room temperature, then argon gas was introduced. Glycosyl donor 15 (12.0 g, 16.6 mmol), dried DCM (200 mL), and DMF (19.3 mL, 249 mmol) were added, and the mixture was stirred at room temperature for 20 minutes. The reaction mixture was then cooled to -78°C, and TfOH (1.5 mL, 16.6 mmol) was added. Subsequent TLC analysis showed that the glycosyl donor had completely disappeared and a new spot had appeared. TBAI (30.7 g, 83.0 mmol) was then added, and TLC analysis showed that the second activation step was complete. The reaction system was placed in an ice-water bath, and glycosyl acceptor 14 (1.6 mL, 13.3 mmol) was added. The temperature was gradually raised to room temperature, and the reaction was carried out at room temperature for 48 hours. TLC analysis showed that the reaction was complete. Triethylamine was added to quench the reaction, and the mixture was diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3 (aq), Na2S2O3 (aq.) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless oil 16 (7.6 g, 83%, / β>20 / 1).1H NMR(400MHz,CDCl3)δ=7.33–7.14(m,15H,ArH),6.83–6.73(m,2H,ArH),4.91(d,J=10.8Hz,1H,PhCH2),4.80(d,J=10.8Hz,1H,PhCH2),4.72(d,J=10.8Hz,1H,PhCH2),4.71(d,J=3.6Hz,1H,1-H),4.63(d,J=11.6Hz,1H,PhCH2),4.52(d,J=10.8Hz,1H,PhCH2),4.49(d,J=10.4Hz,1H,PhCH2),4.28(t,J=6.0Hz,1H,2”-H),4.25–4.14(m,2H,6-H,6’-H),4.00(dd,J=8.4,6.3Hz,1H,1”-H),3.88(t,J=9.2Hz,1H,3-H),3.81–3.74(m,1H,5-H),3.72(s,3H,OMe),3.66(dd,J=8.4,6.1Hz,1H,1”-H),3.53(dd,J=10.6,5.8Hz,1H,3”-H),3.47(dd,J=10.6,5.8Hz,1H,3”-H),3.44(dd,J=9.6,3.6Hz,1H,2-H),3.39(dd,J=10.0,8.8Hz,1H,4-H),2.64(q,J=6.4,5.9Hz,2H,CH2),2.49(t,J=6.6Hz,2H,CH2),2.08(s,3H,CH2),1.34(s,3H,CH3),1.29(s,3H,CH3).13C NMR(100MHz,CDCl3)δ=206.13,172.41,159.36,138.65,137.87,130.18,129.55,128.39,128.35,128.05,127.88,127.80,127.57,113.83,109.40,97.27,81.75,79.57,75.62,75.03,74.51,72.64,69.04,68.82,66.92,63.15,55.21,37.78,29.76,27.74,26.81,25.42.HRMS(ESI)Calcd for C39H52NO11[M+Na]+:710.3535,found:710.3531.。

[0074] Compound 16 (7.6 g, 10.9 mmol) was dissolved in 100 mL of 80% acetic acid aqueous solution and reacted at 85 °C until complete. The reaction solution was concentrated and purified by column chromatography to obtain a colorless oil (6.0 g, 84%). This colorless oil (6.0 g, 9.1 mmol) was dissolved in pyridine (70 mL), and myristoyl chloride (6 mL, 22 mmol) and DMAP (337 mg, 2.8 mmol) were added. The mixture was stirred at room temperature for 12 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with methanol and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with 1N HCl (aq), H2O, NaHCO3 (aq), and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to obtain a colorless oil 17 (8.5 g, 86%). 1 H NMR (400MHz, CDCl3) δ=7.40–7.21(m,14H,ArH),6.88–6.82(m,2H,ArH),5.27–5.20(m,1H,2”-H),4.97(d,J=10.8Hz,1H,PhCH2),4.87(d,J=10.9Hz ,1H,PhCH2),4.80(d,J=10.8Hz,1H,PhCH2),4.671(d,J=11.6Hz,1H,PhCH2),4.670(d,J=3.6Hz,1H,1-H),4.57(d,J=10.8Hz,1H,PhCH2),4.55(d,J =11.6Hz,1H,PhCH2),4.41(dd,J=11.9,3.7Hz,1H,1”-H),4.29(dd,J=11.9,4.5Hz,1H,6-H),4.24–4.17(m,2H,6’-H,1”-H),3.94(t,J=9.3Hz,1H,3 -H),3.80(s,3H,OMe),3.82–3.78(m,1H,5-H),3.74(dd,J=10.8,5.4Hz,1 H,3”-H),3.57–3.42(m,3H,2-H,4-H,3”-H),2.71(q,J=6.4,5.9Hz,2H,CH2 Lev),2.55(t,J=6.6Hz,2H,CH2 Lev),2.29(td,J=7.4,2.2Hz,4H,CH2 myristoyl),2.16(s,3H,CH3 Lev),1.67–1.55(m,4H,CH2myristoyl),1.37–1.19(m,40H,CH2 myristoyl),0.88(t,J=6.7Hz,6H,CH3 myristoyl). 13CNMR(100MHz, CDCl3)δ=206.14,173.28,172.93,172.40,159.34,138.64,137.89,130.22,129.4 3,128.38,128.36,128.05,127.90,127.78,127.58,113.85,97.46,81.64,79.69,75.63,75.00,7 2.72,69.72,68.96,66.31,63.00,62.43,55.20,37.78,34.26,34.08,31.89,29.78,29.66,29.6 5,29.62,29.48,29.33,29.29,29.12,29.11,27.73,24.89,24.88,22.65,14.08.HRMS(ESI)Calcd for C 64 H 100 NO 13 [M+NH4] + :1090.7189,found:1090.7195.

[0075] Compound 17 was dissolved in a DCM / MeOH mixture (9 / 1, 100 mL), and DDQ (3.6 g, 15.6 mmol) was added. The mixture was stirred at room temperature for 5 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with methanol and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3 (aq) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give pale yellow syrup 18 (6.2 g, 82%). 1H NMR(400MHz,CDCl3)δ=7.33–7.28(m,2H,ArH),7.27–7.16(m,8H,ArH),5.22–5.11(m,1H,2”-H),4.89(d,J=11.1Hz,1H,PhCH2),4.79(d,J=10.9Hz,1H,PhCH2),4.744(d,J=10.8Hz,1H,PhCH2),4.735(d,J=3.6Hz,1H,1-H),4.50(d,J=10.9Hz,1H,PhCH2),4.33(dd,J=11.9,4.2Hz,1H,1”-H),4.21(d,J=3.5Hz,2H,6-H,6’-H),4.06(dd,J=11.9,5.9Hz,1H,1”-H),3.80–3.70(m,2H,5-H,3”-H),3.67(t,J=9.0Hz,1H,3-H),3.60(dd,J=9.3,3.8Hz,1H,2-H),3.57–3.47(m,1H,3”-H),3.38(t,J=9.3Hz,1H,4-H),2.62(td,J=6.3,3.9Hz,2H,CH2 Lev),2.48(t,J=6.5Hz,2H,CH2Lev),2.23(m,4H,CH2 myristoyl),2.06(s,3H,CH3 Lev),1.60–1.48(m,4H,CH2 myristoyl),1.19(d,J=9.4Hz,40H,CH2 myristoyl),0.80(t,J=6.7Hz,6H,CH3 myristoyl). 13 C NMR(100MHz,CDCl3)δ=205.87,173.11,172.84,172.20,138.41,137.75,128.24,128.22,127.90,127.78,127.65,127.50,98.89,82.99,76.87,75.21,74.83,72.87,69.70,69.20,66.38,62.84,61.93,37.63,34.13,33.93,31.75,29.56,29.52,29.49,29.33,29.18,29.12,28.97,27.65,24.77,24.73,22.52,13.94.HRMS(ESI)Calcd for C 56 H 92 NO 12 [M+NH4] +:970.6614,found:970.6606.

[0076] Add to reaction flask Molecular sieves were used to prepare a vacuum flask. After cooling to room temperature, argon gas was introduced, and glycosyl donor 19 (6.1 g, 8.1 mmol), dried DCM (100 mL), and DMF (9.5 mL, 121.5 mmol) were added. The mixture was stirred at room temperature for 20 minutes. The reaction mixture was then cooled to -78 °C, and TfOH (0.7 mL, 8.1 mmol) was added. Subsequent TLC analysis showed that the glycosyl donor had completely disappeared and a new spot had appeared. The reaction mixture was then placed in an ice-water bath, and glycosyl acceptor 18 (6.2 g, 6.5 mmol) was added. The temperature was gradually raised to room temperature and the reaction was carried out at room temperature for 24 hours. TLC analysis showed that after the reaction was complete, the reaction was quenched with triethylamine and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3(aq) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless oil 20 (8.4 g, 79%). 1H NMR(400MHz,CDCl3)δ=7.65(d,J=7.2Hz,2H,ArH),7.62(d,J=7.3Hz,2H,ArH),7.43–7.19(m,28H,ArH),7.14–7.05(m,3H,ArH),6.99(t,J=7.5Hz,2H,ArH),5.18–5.12(m,1H,2”-H),5.04(d,J=3.5Hz,1H,1b-H),4.99(d,J=3.4Hz,1H,1a-H),4.96(d,J=10.8Hz,1H,PhCH2),4.94(d,J=10.8Hz,1H,PhCH2),4.88(d,J=11.0Hz,1H,PhCH2),4.86–4.74(m,5H,PhCH2 X 5),4.60(d,J=11.0Hz,1H,PhCH2),4.51(d,J=11.0Hz,1H,PhCH2),4.32(dd,J=12.1,3.2Hz,1H,1”-H),4.25(d,J=3.3Hz,2H,6a-H,6a’-H),4.18(dd,J=12.1,6.2Hz,1H,1”-H),4.07(t,J=9.3Hz,1H,3b-H),3.98(t,J=9.2Hz,1H,3a-H),3.96–3.91(m,H,5b-H),3.85–3.66(m,6H,5a-H,2a-H,3”-H,6b-H,6b’-H,4b-H),3.63–3.54(m,2H,3”-H,2b-H),3.43(t,J=9.4Hz,1H,4a-H),2.73–2.66(m,2H,CH2 Lev),2.54(t,J=6.5Hz,2H,CH2 Lev),2.32–2.20(m,4H,CH2 myristoyl),2.14(s,3H,CH3 Lev),1.64–1.52(m,4H,CH2myristoyl),1.25(t,J=3.9Hz,40H,CH2 myristoyl),1.03(s,9H,tert-Butyl),0.88(t,J=6.7Hz,6H,CH3 myristoyl). 13C NMR (100MHz, CDCl3)δ=206.02,173.16,172.90,172.39,138.61,138.32,138.11,137.87,135.75,135.58,133.53,133.31,129.50,129.47,128 .38,128.35,128.30,128.22,128.14,128.07,128.05,127.93,127.76, 127.72,127.68,127.59,127.54,127.50,127.36,127.29,96.11,94.39, 82.06,80.50,79.71,77.66,77.50,75.89,75.70,75.14,74.99,74.83, 72.74,71.94,69.90,69.14,66.24,63.07,62.70,62.53,37.78,34.23,3 4.04,31.88,29.73,29.66,29.62,29.48,29.47,29.32,29.30,29.27,2 9.11,27.76,26.87,24.91,24.84,22.65,19.26,14.07.HRMS(ESI)Calcd forC 99 H 138 NO 17 Si[M+NH4] + :1641.9762,found:1641.9777.

[0077] Compound 20 (8.4 g, 5.2 mmol) was dissolved in DCM (50 mL), followed by the addition of hydrazine hydrate (250 μL, 5.2 mmol), acetic acid (444 μL, 7.7 mmol), and pyridine (222 μL). The mixture was stirred at room temperature for 5 hours. TLC analysis showed that the reaction was quenched with acetone after completion, and the mixture was diluted with 100 mL of DCM. The organic layer was washed with NaHCO3 (aq) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a semi-solid (6.6 g, 84%). This semi-solid (7.0 g, 4.6 mmol) was dissolved in pyridine (20 mL), followed by the addition of myristoyl chloride (1.5 mL, 5.5 mmol) and DMAP (167 mg, 1.4 mmol). The mixture was stirred at room temperature for 3 hours. TLC analysis showed that the reaction was quenched with methanol after completion, and the mixture was diluted with 100 mL of DCM. The organic layer was washed with 1N HCl (aq), H2O, NaHCO3 (aq), and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless syrup 21 (6.8 g, 86%).1 H NMR(400MHz,CDCl3)δ=7.61–7.51(m,4H,ArH),7.35–7.10(m,28H,2ArH),7.06–6.97(m,3H,ArH),6.96–6.84(m,2H,ArH),5.10–5.03(m,1H,2”-H),4.97(d,J=3.4Hz,1H,1b-H),4.92(d,J=3.2Hz,1H,1a-H),4.89(d,J=10.8Hz,1H,PhCH2),4.87(d,J=10.8Hz,1H,PhCH2),4.80(d,J=11.0Hz,1H,PhCH2),4.77–4.65(m,5H,PhCH2 X 5),4.52(d,J=11.0Hz,1H,PhCH2),4.41(d,J=10.9Hz,1H,PhCH2),4.24(dd,J=12.3,3.2Hz,1H,1”-H),4.17(d,J=3.3Hz,2H,6a-H,6a’-H),4.09(dd,J=12.1,6.2Hz,1H,1”-H),3.99(t,J=9.3Hz,1H,3b-H),3.91(t,J=9.6Hz,1H,3a-H),3.88–3.84(m,2H,5b-H),3.79–3.57(m,6H,3”-H,2a-H,5a-H,4b-H,6b-H,6b’-H),3.56–3.45(m,2H,3”-H,2b-H),3.37(t,J=9.4Hz,1H,4a-H),2.24–2.13(m,6H,CH2 myristoyl),1.51(p,J=7.7,7.1Hz,6H,CH2myristoyl),1.18(d,J=4.8Hz,60H,CH2myristoyl),0.95(s,9H,tert-Butyl),0.81(t,J=6.7Hz,9H,CH3 myristoyl). 13C NMR (100MHz, CDCl3)δ=173.51,173.27,172.97,138.64,138.62,138.36,138.13,137.84,135.82,135.65,133.54,133.34,129.59,129.54,12 8.46,128.40,128.31,128.22,128.18,127.95,127.86,127.84,127.7 8,127.71,127.67,127.64,127.58,127.47,127.39,96.14,94.38,82.1 3,80.58,79.72,77.72,77.60,76.04,75.80,75.14,75.11,74.92,72. 82,71.99,69.90,69.21,66.23,62.77,62.72,62.56,34.29,34.13,34. 11,31.97,29.75,29.73,29.70,29.66,29.56,29.41,29.38,29.36,29. 34,29.22,29.20,26.93,24.98,24.92,22.73,19.33,14.17.HRMS(ESI) . Calcd forC 108 H 158 NO 16 Si[M+NH4] + :1754.1378,found 1754.1359.

[0078] Compound 21 (7.2 g, 4.1 mmol) was dissolved in THF (200 mL), followed by the addition of 70% pyridine hydrofluoride solution (41 mL). The mixture was stirred at room temperature for 12 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with NaHCO3 (aq) and diluted with 200 mL of DCM. The organic layer was separated by NH4Cl (aq), washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless oil 3-1 (5.0 g, 80%). 1H NMR(400MHz,CDCl3)δ=7.39–7.22(m,22H,ArH),7.22–7.10(m,3H,ArH),5.18–5.11(m,1H,2”-H),4.97(d,J=10.8Hz,1H,PhCH2),4.95(d,J=3.2Hz,1H,1b-H),4.948(d,J=3.6Hz,1H,1a-H),4.935(d,J=10.4Hz,1H,PhCH2),4.87(d,J=11.2Hz,2H,PhCH2 X 2),4.85(d,J=11.2Hz,1H,PhCH2),4.83(d,J=11.2Hz,1H,PhCH2),4.77(d,J=11.9Hz,1H,PhCH2),4.72(d,J=11.9Hz,1H,PhCH2),4.61(d,J=11.2Hz,1H,PhCH2),4.55(d,J=10.8Hz,1H,PhCH2),4.33(dd,J=12.3,3.2Hz,1H,1”-H),4.30–4.25(m,2H,6a-H,6a’-H),4.19(dd,J=12.2,6.3Hz,1H,1”-H),4.06(t,J=9.3Hz,1H,3b-H),3.99(t,J=9.3Hz,1H,3a-H),3.94–3.80(m,2H,2H,5b-H,5a-H),3.79–3.68(m,2H,3”-H,2a-H),3.59–3.45(m,6H,3”-H,4a-H,2b-H,4b-H,6b-H,6b’-H),2.36–2.20(m,6H,CH2myristoyl),1.66–1.51(m,6H,CH2 myristoyl),1.35–1.16(m,60H,CH2 myristoyl),0.88(t,J=6.7Hz,9H,CH3 myristoyl). 13C NMR (100MHz, CDCl3)δ=173.40,173.20,172.88,138.59,138.38,138.06,137.97,137.68,128.43,128.37,12 8.30,128.28,128.06,127.87,127.81,127.79,127.64,127.61,127.52,96.32,95.48,81.83,80.41,79.32, 77.77,77.25,76.13,75.98,75.53,75.13,74.86,73.01,71.33,69.77,69.20,66.33,34.22,34.08,34.04,3 1.89,29.65,29.64,29.48,29.33,29.28,29.15,29.12,24.90,24.88,24.85,22.65,14.09.HRMS(ESI)Calcd for C 92 H 136 NaO 16 [M+Na] + :1519.9721,found1519.9792.

[0079] 3. Preparation of compound 3-2

[0080]

[0081] Add to reaction flask Molecular sieves were used. The mixture was vacuum-sealed in a flask, cooled to room temperature, and then purged with argon gas. Glycosyl donor 22 (10.0 g, 14.0 mmol), dried DCM (168 mL), and DMF (16.2 mL, 210 mmol) were added, and the mixture was stirred at room temperature for 20 minutes. The reaction mixture was then cooled to -78°C, and TfOH (1.2 mL, 14.0 mmol) was added. Subsequent TLC analysis showed that the glycosyl donor had completely disappeared and a new spot had appeared. TBAI (25.8 g, 70.0 mmol) was then added, and TLC analysis showed that the second activation step was complete. The reaction mixture was placed in an ice-water bath, and glycosyl acceptor 14 (1.4 mL, 11.2 mmol) was added. The temperature was gradually raised to room temperature, and the reaction was allowed to proceed for 24 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with triethylamine and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3 (aq), Na2S2O3 (aq.) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless oil 23 (6.1 g, 80%, α / β > 20 / 1).1H NMR(400MHz,CDCl3)δ=7.39–7.21(m,16H,ArH),7.18–7.11(m,2H,ArH),6.84(d,J=8.5Hz,2H,ArH),4.97(d,J=10.9Hz,1H,PhCH2),4.83(d,J=11.6Hz,1H,PhCH2),4.81(d,J=2.8Hz,1H,1-H),4.79(d,J=11.2Hz,1H,PhCH2),4.70(d,J=11.7Hz,1H,PhCH2),4.59(d,J=12.4Hz,1H,PhCH2),4.58(d,J=11.6Hz,1H,PhCH2),4.47(d,J=11.2Hz,1H,PhCH2),4.46(d,J=12.0Hz,1H,PhCH2),4.35(t,J=6.0Hz,1H,2”-H),4.05(dd,J=8.4,6.3Hz,1H,3”-H),3.94(t,J=9.3Hz,1H,3-H),3.83–3.68(m,3H,3”-H,5-H,6-H,),3.75(s,3H,OMe),3.68–3.50(m,5H,2-H,4-H,1”-H X 2,6-H),1.41(s,3H,CH3),1.35(s,3H,CH3).13C NMR(100MHz,CDCl3)δ=159.23,138.73,138.11,137.76,130.17,129.47,128.20,127.76,127.74,127.71,127.52,127.39,113.69,109.26,97.36,81.75,79.49,77.45,75.48,74.89,74.43,73.31,72.55,70.18,68.91,68.34,66.88,55.07,26.70,25.32.HRMS(ESI)Calcd for C41H48KO9[M+K]+:723.2930,found 723.2927;Calcd for C41H52NO9[M+NH4]+:702.3637,found:702.3642.。

[0082] Compound 23 (7.0 g, 10.2 mmol) was dissolved in 100 mL of 80% acetic acid aqueous solution and reacted at 85 °C until complete. The reaction solution was concentrated and purified by column chromatography to obtain a colorless oil (5.5 g, 83%). This colorless oil (5.0 g, 8.5 mmol) was dissolved in pyridine (40 mL), and myristoyl chloride (5 mL, 18.6 mmol) and DMAP (283 mg, 2.3 mmol) were added. The mixture was stirred at room temperature for 12 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with methanol and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with 1N HCl (aq), H2O, NaHCO3 (aq), and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to obtain a colorless oil 24 (6.5 g, 81%). 1 H NMR (400MHz, CDCl3) δ=7.36–7.22(m,16H,ArH),7.16–7.10(m,2H,ArH),6.85(d,J=8 .1Hz,2H,ArH),5.28–5.21(m,1H,2”-H),4.95(d,J=10.8Hz,1H,PhCH2),4.82(d,J=1 1.2Hz,1H,PhCH2),4.78(d,J=10.8Hz,1H,PhCH2),4.70(d,J=3.6Hz,1H,1-H),4.68( d,J=11.2Hz,1H,PhCH2)4.59(d,J=12.4Hz,1H,PhCH2),4.55(d,J=11.6Hz,1H,PhCH2) ,4.47(d,J=10.8Hz,1H,PhCH2),4.45(d,J=12.4Hz,1H,PhCH2),4.40(dd,J=12.0,3. 5Hz,1H,1”-H),4.18(dd,J=12.0,6.0Hz,1H,1”-H),3.91(t,J=9.2Hz,1H,3-H),3.80 (s,3H,OMe),3.77–3.67(m,3H,3”-H,5-H,6a-H),3.67–3.59(m,2H,4-H,6b-H),3.59 –3.49(m,2H,2-H,3”-H),2.28(t,J=7.7Hz,4H,CH2myristoyl),1.70–1.51(m,4H,CH2 myristoyl), 1.25 (s, 40H, CH2 myristoyl), 0.88 (t, J = 6.6Hz, 6H, CH3 myristoyl). 13C NMR (100MHz, CDCl3) δ=172.97,172.64,159.17,138.68,138.10,137.70,130.17,129.26,128.12,1 28.07,127.68,127.62,127.61,127.44,127.38,127.28,113.64,97.57,81.60,79.61,77.32,75.4 0,74.79,73.27,72.56,70.36,69.63,68.24,66.16,62.26,54.92,34.07,33.88,31.73,29.51,29. 47,29.46,29.45,29.31,29.17,29.11,28.94,28.92,24.72,24.70,22.50,13.94.HRMS(ESI)Calcd for C 66 H 100 NO 11 [M+NH4] + :1082.7291,found 1082.7304.Calcd for C 66 H 96 KO 11 [M+K] + :1103.6584,found1103.6581

[0083] Compound 24 was dissolved in a DCM / MeOH mixture (9 / 1, 100 mL), and DDQ (2.6 g, 11.2 mmol) was added. The mixture was stirred at room temperature for 5 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with methanol and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3 (aq) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give pale yellow syrup 25 (4.9 g, 94%). 1H NMR(400MHz,CDCl3)δ=7.39–7.35(m,2H,ArH),7.35–7.25(m,12H,ArH),7.17–7.12(m,2H,ArH),5.29–5.21(m,1H,2”-H),4.94(d,J=11.1Hz,1H,PhCH2),4.87(d,J=3.2Hz,1H,1-H),4.82(d,J=11.2Hz,2H,PhCH2 X 2),4.61(d,J=12.1Hz,1H,PhCH2),4.49(d,J=11.6Hz,2H,PhCH2 X 2),4.38(dd,J=11.9,4.2Hz,1H,3”-H),4.11(dd,J=11.9,5.7Hz,1H,3”-H),3.84(dd,J=11.0,4.5Hz,1H,1”-H),3.77–3.70(m,4H,2-H,3-H,5-H,6-H),3.68–3.59(m,3H,3”-H,4-H,6’-H),2.36–2.24(m,4H,CH2myristoyl),1.66–1.54(m,4H,CH2 myristoyl),1.37–1.23(m,40H,CH2 myristoyl),0.88(t,J=6.6Hz,6H,CH3 myristoyl). 13 C NMR(100MHz,CDCl3)δ=173.34,173.08,138.61,138.13,137.83,128.36,128.33,127.92,127.82,127.69,127.67,127.63,99.21,83.23,77.14,75.38,74.98,73.52,72.97,70.92,69.83,68.36,66.57,34.27,34.08,31.90,29.67,29.64,29.62,29.48,29.47,29.34,29.27,29.11,24.89,24.87,22.67,14.10.HRMS(ESI)Calcd for C 58 H 92 NO 10 [M+NH4] + :962.6716,found:962.6706.Calcd for C 58 H 88 NaO 10 [M+Na] + :967.6270,found:967.6212.

[0084] Add to reaction flask Molecular sieves were used to vacuum-sterilize a flask. After cooling to room temperature, argon gas was introduced, and glycosyl donor 19 (4.0 g, 4.8 mmol), dried DCM (60 mL), and DMF (5.6 mL, 72.0 mmol) were added. The mixture was stirred at room temperature for 20 minutes. The reaction mixture was then cooled to -78°C, and TfOH (0.4 mL, 4.8 mmol) was added. Subsequent TLC analysis showed that the glycosyl donor had completely disappeared and a new spot had appeared. The reaction mixture was then placed in an ice-water bath, and glycosyl acceptor 25 (3.6 g, 3.8 mmol) was added. The temperature was gradually raised to room temperature and reacted at room temperature for 24 hours. TLC analysis showed that after the reaction was complete, the reaction was quenched with triethylamine and diluted with 200 mL of DCM. The precipitate was filtered through a diatomaceous earth filter. The organic layer was washed with NaHCO3(aq) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless oil 26 (5.0 g, 80%). 1H NMR(400MHz,CDCl3)δ=7.68–7.60(m,4H,ArH),7.43–7.20(m,32H,ArH),7.13–7.03(m,5H,ArH),6.99–6.92(m,2H,ArH),5.19–5.12(m,1H,2”-H),5.03(d,J=4.0Hz,1H,1b-H),5.02(d,J=2.8Hz,1H,1a-H),4.95(d,J=10.8Hz,1H,PhCH2),4.92(d,J=11.8Hz,1H,PhCH2),4.89(d,J=10.4Hz,1H,PhCH2),4.85–4.71(m,5H,PhCH2 X 5),4.61(d,J=12.0Hz,1H,PhCH2),4.59(d,J=10.8Hz,1H,PhCH2),4.47(d,J=13.2Hz,1H,PhCH2),4.43(d,J=10.0Hz,1H,PhCH2),4.32(dd,J=12.1,3.3Hz,1H,1”-H),4.16(dd,J=12.1,6.1Hz,1H,1”-H),4.08(t,J=9.2Hz,1H,3b-H),4.02–3.91(m,2H,5b-H,3a-H),3.85–3.55(m,11H,3”-H X 2,2b-H,4b-H,6b-H,6b’-H,2a-H,4a-H,5a-H,6a-H,6a’-H),2.30–2.20(m,4H,CH2 myristoyl),1.61–1.51(m,4H,CH2 myristoyl),1.30–1.22(m,40H,CH2 myristoyl),1.02(s,9H,tert-Butyl),0.88(t,J=6.5Hz,6H,CH3 myristoyl). 13C NMR (100MHz, CDCl3)δ=173.21,172.93,138.67,138.63,138.37,138.24,138.21,137.88,135.76,135.61,133.55,133.29,129.48,1 29.45,128.38,128.32,128.26,128.18,128.14,128.11,128.05,127.81,127.71,127.67,127.62,127.58,127.56,127.55,127.51,1 27.28,96.37,94.45,82.11,80.52,79.74,77.70,77.61,75.87,75.73,75.22,74.96,74.83,73.45,72.74,71.80,70.74,69.96,68.4 4,34.24,34.05,31.90,29.68,29.66,29.64,29.49,29.34,29.31,29.30,29.13,26.86,24.90,24.85,22.67,14.10.HRMS(ESI)Calcd for C 101 H 138 NO 15 Si[M+NH4] + :1633.9864,found:1633.9859.

[0085] Compound 26 (4.3 g, 2.7 mmol) was dissolved in THF (100 mL), followed by the addition of 70% pyridine hydrofluoride solution (26 mL). The mixture was stirred at room temperature for 12 hours. TLC analysis showed that the reaction was complete. The reaction was quenched with NaHCO3 (aq) and diluted with 200 mL of LDM. The organic layer was separated by NH4Cl (aq), washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a colorless oil 3-2 (3.2 g, 87%). 1H NMR(600MHz,CDCl3)δ=7.31–7.13(m,26H,ArH),7.13–7.08(m,1H,ArH),7.07–7.00(m,4H,ArH),5.11–5.05(m,1H,2”-H),4.90(d,J=3.8Hz,1H,1a-H),4.89(4.87 4.90(d,J=11.4Hz,1H,PhCH2),(d,J=3.6Hz,1H,1b-H),4.83(d,J=10.7Hz,1H,PhCH2),4.79(d,J=11.2Hz,1H,PhCH2),4.76(d,J=11.4Hz,2H,PhCH2 X 2),4.74(d,J=10.8Hz,1H,PhCH2),4.68(d,J=11.9Hz,1H,PhCH2),4.64(d,J=11.9Hz,1H,PhCH2),4.53(d,J=11.6Hz,1H,PhCH2),4.52(d,J=12.0Hz,1H,PhCH2),4.41(d,J=11.6Hz,1H,PhCH2),4.40(d,J=12.0Hz,1H,PhCH2),4.25(dd,J=12.1,3.2Hz,1H,1”-H),4.10(dd,J=12.1,6.3Hz,1H,1”-H),3.98(t,J=9.3Hz,1H,3b-H),3.89(t,J=9.4Hz,1H,3a-H),3.81(dt,J=10.1,3.0Hz,1H,5a-H)3.71–3.62(m,4H,3”-H,6b-H,2b-H,5b-H),3.59(t,J=9.5Hz,1H,4b-H),3.56(dd,J=10.7,2.0Hz,1H,6b’-H),3.51–3.39(m,5H,4a-H,3”-H,6a-H,6a’-H,2a-H),2.19(t,J=7.6Hz,2H,CH2 myristoyl),2.15(t,J=7.6Hz,2H,CH2myristoyl),1.49(dt,J=13.0,7.2Hz,4H,CH2 myristoyl),1.27–1.07(m,40H,CH2myristoyl),0.80(t,J=7.0Hz,6H,CH3 myristoyl). 13C NMR (100MHz, CDCl3)δ=173.12,172.84,138.65,138.60,138.40,138.13,138.07,137.78,137.72,128.35,128.28,128.22,128.19,12 7.97,127.83,127.83,127.80,127.76,127.70,127.63,127.61,127.53,127.47,127.44,127.41,96.49,95.34,81.82,81.78,80.38, 79.33,77.84,77.82,77.79,77.19,76.06,75.83,75.44,74.93,74.76,73.42,72.88,71.17,70.70,69.84,68.20,66.35,62.53,61.2 3,34.17,33.98,31.90,31.82,29.60,29.56,29.41,29.26,29.23,29.20,29.04,24.84,24.77,24.76,22.59,14.04.HRMS(ESI)Calcd for C 85 H 120 NO 15 [M+NH4] +: 1394.8652, found: 1394.8662.

[0086] 4. Preparation of compound 5-1

[0087]

[0088] Add to reaction flask Molecular sieves were used in a vacuum flask. After cooling to room temperature, argon gas was introduced. 1 (1.0 g, 0.64 mmol) and N,N-diisopropylammonium tetrazolium salt (218 mg, 1.27 mmol) were dissolved in a dry 6.4 mL DCM solution and stirred at room temperature for 20 minutes. Then, 2-cyanoethyl N,N,N,N-tetraisopropylphosphonic diamine (303 μL, 0.96 mmol) was added, and stirring continued for 6 hours. TLC analysis showed that after the reaction was complete, the precipitate was filtered through a diatomaceous earth filter. The organic phase was washed with NaHCO3(aq) and brine, dried over Na2SO4, filtered, and concentrated to obtain a semi-solid product 2-1, which was used directly in the next synthesis without purification. Argon gas was added to the reaction flask. Molecular sieves were vacuum-sealed in flasks, cooled to room temperature, and then purged with argon gas. Freshly prepared 2 (1.1 g, 0.64 mmol) and 3-1 (666 mg, 0.444 mmol) were added and dissolved in 6.4 mL of dry DCM. Tetraazole (89 mg, 1.27 mmol) was then added and the mixture was stirred at room temperature for 2 hours. TLC analysis showed that the starting material had completely disappeared. The reaction mixture was then placed in an ice-water bath, and peroxide tert-butanol (120 μL) was added. Stirring was continued for 3 hours. TLC analysis showed that the reaction was complete, and the molecular sieves were filtered through a diatomaceous earth filter. The mixture was washed with NaHCO3(aq) and brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography to give a pair of diastereomers 4-1 (1.07 g, 76%). 1 H NMR (600MHz, CDCl3, mixture of diastereoisomers) δ = 7.28–6.95 (m, 80H, ArH), 5.31 (s, 1H, anomeric H), 5.15 (d, J = 3.6Hz, 1H, anomeric H), 5.03–5.00 (m, 1H, 2-H Gro),4.89(d,J=3.7Hz,1H,anomeric H),4.88–4.85(m,1H),4.84–4.13(m,44H),4.11–4.08(m,2H),4.06–3. 70(m,25H),3.68–3.58(m,4H),3.54–3.31(m,11H),2.24–2.13(m,6H,3x CH2 myristoyl),2.12–2.04(m,1H,CH2cyanoethyl),1.86(t,J=6.0Hz,1H,3x CH2 cyanoethyl),1.55–1.44(m,6H,3x CH2myristoyl),1.31–1.02(m,60H,30x CH2 myristoyl),0.80(t,J=7.0Hz,9H,3xCH3myristoyl). 13 C NMR (150MHz, CDCl) 3,mixture of diastereoisomers)δ=173.42,173.16,172.81,138.90,138.86,138.84,138.78,138.65,138.20,138.14,138.03,128.43,128.41,128.39,128.37,128.35,128.32,128.30,128.27,128.24,128.22,128.15,128.13,128.02,127.90,127.85,127.83,127.79,127.77,127.73,127.70,127.66,127.46,127.42,127.40,127.35,127.30,127.26,116.66,98.79,98.66,98.43,98.30,96.20,96.01,95.76,95.43,95.33,81.64,80.31,79.58,79.50,79.44,79.16,79.01,78.95,78.21,78.13,76.28,76.07,75.89,75.49,75.25,75.10,74.98,74.79,74.64,73.77,73.46,73.43,73.36,73.32,73.06,72.98,72.95,72.90,72.77,72.63,69.81,69.68,69.54,69.32,69.02,68.82,67.11,66.45,62.04,61.85,34.26,34.08,31.91,29.69,29.66,29.64,29.51,29.33,29.30,29.20,29.16,24.95,24.90,24.88,22.66,14.07. 31 P NMR(202MHz,CDCl3,mixture of diastereoisomers)δ=-0.77,-0.91.HRMS(MALDI-TOF)Calcd forC 193 H 242 NNaO 36 P[M+Na] + :3205.6834,found:3205.682.

[0089] Compound 4-1 (170 mg, 0.05 mmol) was dissolved in DCM (20 mL), one drop of DBU was added, and the mixture was stirred at room temperature for 30 minutes until TLC analysis showed that the starting material had completely disappeared. The product was purified by silica gel column chromatography. The resulting product was dissolved in a mixture of EtOAc / THF / EtOH / H2O (4 / 2 / 1 / 1, 8 mL), and 10% palladium / carbon (30 mg) was added. The product was catalytically hydrogenated for 3 days until TLC analysis showed that the starting material had completely disappeared. The precipitate was removed by filtration through diatomaceous earth and filter paper, and the mixture was concentrated. A mixture of CHCl3 / MeOH / H2O (65 / 50 / 7, 20 mL) was added, and the precipitate was collected. This product was 5-1 (39.5 mg, 44%). 1 H NMR (600MHz, CDCl3 / CD3OD / D2O 20 / 9 / 2, v / v / v) δ=5.14(dq,J=9.1,3.8,3.3Hz,1H,2-HGro),5.05(d,J=3.8Hz,1H,anomeric H),4.90(d,J=3.5Hz,1H,anomeric H),4.86–4.79(m,3H,3x anomeric H),4.37–4.35(m,1H,CH2),4.30(d,J=11.6Hz,1H,CH2),4.18–4.08(m,2H,2x CH2),4.04–3.89(m,10H),3.87–3.76(m,5H),3.76–3.59(m,13H),3.57– 3.49(m,4H),3.40–3.37(m,2H),3.25–3.22(m,1H),2.28–2.21(m,6H,3x CH2 myristoyl), 1.54–1.50 (m, 6H, 3x CH2 myristoyl), 1.21–1.18 (m, 60H, 30x CH2 myristoyl), 0.79 (t, J = 6.9Hz, 9H, 3x CH3 myristoyl). 13C NMR (150MHz, CDCl3 / CD3OD / D2O20 / 9 / 2, v / v / v)δ=174.37,174.16,173.56,99.07,98.54,98.21,97.11, 96.01,76.31,75.56,73.13,71.75,71.06,70.82,70.54,70.05,69.87,69.80,69.74,69.63,69.49,69 .39,69.14,68.77,68.51,67.14,66.76,65.50,64.13,62.78,61.34,34.19,34.08,34.04,31.80,29.57,29.55,29.53,29.49,29.44,29.26,29.24,29.22,29.13,29.09,29.05,24.86,24.81,22.52,13.75. 31 P NMR(202MHz,CDCl3 / CD3OD / D2O 20 / 9 / 2,v / v / v)δ=0.55.HRMS(MALDI-TOF)Calcd for C 78 H 142 Na2O 36 P[M+2Na] + :1731.8808,found:1731.880.

[0090] 5. Preparation of compound 5-2

[0091] Compound 5-2 was prepared using the same method as compound 5-1. 11H NMR (600 MHz, CDCl3 / CD3OD / D2O 30 / 13 / 2, v / v / v) δ = 5.15 (dt, J = 8.5, 4.2 Hz, 1H, 2-H Gro), 5.07 (s, 1H, anomeric H), 4.96 (d, J = 3.4 Hz, 1H, anomeric H), 4.90–4.81 (m, 3H, 3x anomeric H), 4.40–4.35 (m, 1H, CH2), 4.14–4.13 (m, 1H, CH2), 4.01–3.82 (m, 14H), 3.79–3.49 (m, 19H), 3.46–3.34 (m, 4H), 2.26–2.20 (m, 4H, 2x CH2 myristoyl), 1.54–1.48 (m, 4H, 2x CH2 myristoyl), 1.25–1.15 (m, 40H, 20x CH2 myristoyl), 0.79 (t, J = 6.9 Hz, 6H, 2x CH3 myristoyl). 13 13C NMR (125 MHz, CDCl3 / CD3OD / D2O 30 / 13 / 2, v / v / v) δ = 174.32, 173.88, 98.97, 98.55, 98.05, 96.57, 96.25, 75.79, 75.65, 73.05, 72.14, 71.69, 71.66, 71.56, 71.06, 71.06, 70.99, 70.85, 70.85, 69.98, 69.73, 69.73, 69.62, 69.62, 69.47, 69.46, 69.13, 69.00, 68.56, 68.56, 68.35, 66.95, 66.71, 65.82, 64.53, 64.53, 62.91, 61.31, 60.44, 49.27, 34.21, 34.08, 31.81, 29.59, 29.54, 29.46, 29.28, 29.23, 29.09, 29.05, 24.88, 24.81, 22.53, 13.77. 31 31P NMR (202 MHz, CDCl3 / CD3OD / D2O 30 / 13 / 2, v / v / v) δ = 0.62. HRMS (MALDI-TOF) Calcd for C 64 H 116 Na2O 35 P [M + 2Na] + : 1521.6825, found: 1521.686.

[0092] Preparation of Compound 5-3

[0093] Compound 5-3 was prepared using the same method as compound 5-1. 1 H NMR (600MHz, CDCl3 / CD3OD / D2O20 / 9 / 2, v / v / v)δ=5.17–5.12(m,1H,2-H Gro),5.08(s,1H,anomeric H),4.91(d,J=3.5Hz,1H,anomeric H),4.86–4.85(m,2H,anomeric H),4.83(d,J=3.5Hz,1H,anomeric H),4.39–4.34(m,1H,CH2),4.33–4.30(m,1H,CH2),4.17(dd,J=12.2,6.5Hz,1H,CH2),4.11(dd,J=11.8,7.9Hz ,1H,CH2),4.08–3.78(m,13H),3.77–3.49(m,19H),3.39–3.33(m,2H),3.28–3.26(m,1H),2.27–2.24(m,6H,3x CH2 myristoyl),1.56–1.50(m,6H,3x CH2 myristoyl),1.26–1.16(m,60H,30x CH2 myristoyl),0.79(t,J=7.0Hz,9H,3x CH3 myristoyl). 13 CNMR(125MHz,CDCl3 / CD3OD / D2O 20 / 9 / 2,v / v / v)δ=174.08,173.87,173.25,98.38,97.79,97.23,96.73,95.64,75.91,74.08,7 2.75,71.42,70.84,70.53,70.18,69.70,69.60,69.51,69.34,69.27,69.17,69.00,68.66,68. 35,68.15,67.14,66.15,65.13,63.83,62.44,61.08,60.98,33.86,33.75,33.71,31.48,29.25,29.23,29.21,29.18,29.12,28.94,28.90,28.80,28.77,28.73,24.53,24.49,22.20,13.45. 31 P NMR(202MHz,CDCl3 / CD3OD / D2O 20 / 9 / 2,v / v / v)δ=0.96.HRMS(MALDI-TOF)Calcd for C 78 H 142Na2O 36 P[M+2Na] + :1731.8808,found:1731.873.

[0094] 7. Preparation of compounds 5-4

[0095] Compound 5-4 was prepared using the same method as compound 5-1. 1 H NMR (600MHz, CDCl3 / CD3OD / D2O30 / 20 / 6, v / v / v)δ=5.15(qd,J=5.8,2.6Hz,1H,2-H Gro),5.07(d,J=2.9Hz,1H,anomericH),4.95(d,J=3.4Hz,1H,anomeric H),4.88(d,J=3.8Hz,1H,anomeric H),4.83–4.82(m,2H,anomeric H),4.36(dd,J=12.2,2.7Hz,1H,CH2),4.13–4.12(m,1H,CH2),4.09–3.89(m,8H),3.89–3.51(m,25 H),3.46–3.43(m,2H),3.42–3.34(m,2H),2.25–2.21(m,4H,2xCH2myristoyl),1.53–1.48(m,4H,2x CH2 myristoyl), 1.22–1.14 (m, 40H, 20x CH2 myristoyl), 0.79 (t, J = 6.9Hz, 6H, 2x CH3 myristoyl). 13 C NMR (150MHz, CDCl3 / CD3OD / D2O30 / 20 / 6, v / v / v)δ=173.90,173.48,98.35,97.76,97.21,96.21,95.9 0,75.50,72.78,71.78,71.39,71.29,70.82,70.74,70.47,69.66,69.58,69.49,69.34,69.25,69.15 ,68.93,68.65,68.32,68.13,67.11,66.16,65.44,62.49,61.06,60.94,60.26,33.81,33.67,31.40,29.16,29.14,29.12,29.04,29.02,28.85,28.81,28.66,28.62,24.47,24.40,22.11,13.32,13.31. 31P NMR(202MHz,CDCl3 / CD3OD / D2O 30 / 20 / 6,v / v / v)δ=0.62.HRMS(MALDI-TOF)Calcd for C 64 H 116 Na2O 35 P[M+2Na] + :1521.6825,found:1521.695.

[0096] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A compound, characterized in that, It is selected from the compounds shown in Formula I below. Wherein, X is independently selected from: H or a fatty acyl group, wherein the fatty acyl group is -COC. 13 H 27 .

2. A pharmaceutically acceptable salt of the compound of claim 1.

3. A method for preparing the compound according to any one of claims 1-2, characterized in that, The synthetic route for the compound shown in Formula I includes: 。 4. The preparation method according to claim 3, characterized in that, The preparation method includes: S1, Compound 1 and N , N After reacting diisopropylammonium tetrazolium salt at room temperature for a period of time, 2-cyanoethyl salt is added. N , N , N , N - The reaction of tetraisopropylphosphonium diamine continued until complete, and the mixture was filtered and concentrated to obtain a semi-solid product 2, which was used directly in the next step of synthesis without purification. S2. Compound 2 and compound 3 were reacted under tetrazolium conditions until the starting material was completely eliminated. The reaction system was placed in an ice-water bath, peroxytert-butanol was added and the mixture was stirred until the reaction was complete. Compound 4 was obtained by purification. S3. Compound 5 is obtained by removing the protecting group from compound 4.

5. The preparation method according to claim 4, characterized in that, The compound 1 is either compound 1-1 or compound 1-2; the compound 3 is either compound 3-1 or compound 3-2; 。 6. The preparation method according to claim 4, characterized in that, The compound 4 is compound 4-1, compound 4-2, compound 4-3 or compound 4-4, and the compound 5 is compound 5-1, compound 5-2, compound 5-3 or compound 5-4; 。 7. The preparation method according to claim 5, characterized in that, Compound 1 was prepared by a glycosylation method based on a pre-activated O-glycosyltrichloroacetimide ester donor; When compound 1 is compound 1-1, its synthetic route is as follows: The steps include: (1) Compound 6 and Compound 7 are glycosylated using a pre-activated O-glycosyl trichloroacetylimine ester donor glycosylation method to prepare Compound 8; (2) Compound 8 is deprotected by an allyl group to obtain Compound 9-1, and then glycosylated with Compound 10 using a pre-activated O-glycosyl trichloroacetylimine ester donor glycosylation method to prepare Compound 11-1; (3) Compound 11-1 is deprotected by a TBDPS protecting group to obtain Compound 12-1, and then glycosylated with Compound 7 using a pre-activated O-glycosyl trichloroacetylimine ester donor glycosylation method to prepare Compound 13-1; (4) Compound 13-1 is deprotected by a Bz protecting group to obtain Compound 1-1. When compound 1 is compound 1-2, its synthetic route is as follows: The steps include: (1) Compound 6 and Compound 7 are glycosylated using a pre-activated O-glycosyl trichloroacetilime ester donor glycosylation method to prepare Compound 8; (2) Compound 8 is deprotected by the Bz protecting group to obtain Compound 9-2, and then Compound 9-2 is prepared by glycosylation using a pre-activated O-glycosyl trichloroacetilime ester donor glycosylation method with Compound 10; (3) Compound 9-2 is deprotected by the TBDPS protecting group to obtain Compound 12-2, and then Compound 9-2 is prepared by glycosylation using a pre-activated O-glycosyl trichloroacetilime ester donor glycosylation method with Compound 7; (4) Compound 9-2 is deprotected by the allyl group to obtain Compound 1-2.

8. The preparation method according to claim 5, characterized in that, Compound 3 was prepared by a glycosylation method based on a pre-activated O-glycosyltrichloroacetimide ester donor; When compound 3 is compound 3-1, its synthetic route is as follows: The steps include: (1) Compound 14 and Compound 15 are glycosylated using a pre-activated O-glycosyl trichloroacetylimide ester donor to prepare Compound 16; (2) Compound 16 is deprotected and myristylated to obtain Compound 17, which is then glycosylated with Compound 19 using a pre-activated O-glycosyl trichloroacetylimide ester donor to prepare Compound 20; (3) Compound 20 is deprotected by the Lev protecting group and myristylated to obtain Compound 21; (4) Compound 21 is deprotected by the TBDPS protecting group to obtain Compound 3-1. When compound 3 is compound 3-2, its synthetic route is as follows: The steps include: (1) Compound 14 and Compound 22 are glycosylated using a pre-activated O-glycosyl trichloroacetylimide ester donor to prepare Compound 23; (2) Compound 23 is deprotected and myristylated to obtain Compound 24, which is then glycosylated with Compound 19 using a pre-activated O-glycosyl trichloroacetylimide ester donor to prepare Compound 25; (3) Compound 25 is deprotected using a TBDPS protecting group to obtain Compound 3-2.

9. A composition, characterized in that, The composition comprises the compound according to any one of claims 1-2.

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