Glycosyl donor, preparation method therefor, and use thereof

Abstract

A glycosyl donor represented by formula (I) is used for preparing an S-glycoside compound represented by formula (III), an O-glycoside compound represented by formula (V), and a C-glycoside compound represented by formula (V). The glycosyl donor is a raw material in the preparation of O-glycoside, S-glycoside, and C-glycoside compounds by means of a free radical reaction, most of which have a special configuration.

Claims

1. A glycosyl donor, or a salt thereof, or a stereoisomer thereof, or an optical isomer thereof, wherein the glycosyl donor is of formula I: ##STR00150## wherein, ring A is ##STR00151## wherein, in ring A, each of R.sup.2, R.sup.3, and R.sup.4 is independently selected from the group consisting of H, C.sub.1-6 alkyl, aryl substituted C.sub.1-12 alkyl, heteroaryl substituted C.sub.1-12 alkyl, C.sub.1-12 alkoxyl, C.sub.2-8 alkynyl, C.sub.2-8 alkenyl, aryl, heteroaryl, cycloalkyl, M.sub.1OH, M.sub.1NH.sub.2, M.sub.1NHAc, M.sub.1OAc, M.sub.1OBz, M.sub.1OBn, M.sub.1N.sub.3, M.sub.1OTMS, M.sub.1OTBS, ##STR00152## and M.sub.1 is 0-3 methylene, while R.sup.1 is M.sub.1OAc and M.sub.1 is 1-3 methylene, or R.sup.1 is selected from the group consisting of H, C.sub.1-6 alkyl, aryl substituted C.sub.1-12 alkyl, heteroaryl substituted C.sub.1-12 alkyl, C.sub.1-12 alkoxyl, C.sub.2-8 alkynyl, C.sub.2-8 alkenyl, aryl, heteroaryl, cycloalkyl, M.sub.1OH, M.sub.1NH.sub.2, M.sub.1NHAc, M.sub.1OBz, M.sub.1OBn, M.sub.1N.sub.3, M.sub.1OTMS, M.sub.1OTBS, ##STR00153## and M.sub.1 is 0-3 methylene; or any two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are linked to form a ring; wherein M.sub.2, M.sub.3, M.sub.4 are selected from the group consisting of H, C.sub.1-6 alkyl, aryl substituted C.sub.1-12 alkyl, heteroaryl substituted C.sub.1-12 alkyl, C.sub.2-8 alkynyl, C.sub.2-8 alkenyl, aryl, heteroaryl, or M.sub.3 and M.sub.4 are linked to form a ring; R.sup.5 is selected from the group consisting of C.sub.1-10 alkyl, saturated cycloalkyl, saturated heterocyclyl, aryl, heteroaryl, C.sub.1-10 alkoxyl, halogen, cyano, carboxyl, and ester group; and each of R.sup.6, R.sup.7, R.sup.8, and R.sup.9 is independently selected from the group consisting of H, halogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxyl, M.sub.1OH, C.sub.2-8 alkynyl, C.sub.2-8 alkenyl, saturated cycloalkyl, saturated heterocyclyl, H, aryl, heteroaryl, cyano, and ester group.

2. The glycosyl donor according to claim 1, or a salt thereof, or a stereoisomer thereof, or an optical isomer thereof, wherein the glycosyl donor has a structure of formula II-1 or II-2: ##STR00154## wherein, each of R.sup.2, R.sup.3, and R.sup.4 is selected from the group consisting of H, C.sub.1-6 alkyl, C.sub.1-6 alkoxyl, C.sub.2-6 alkynyl, C.sub.2-6 alkenyl, aryl, heteroaryl, cycloalkyl, M.sub.1OH, M.sub.1NH.sub.2, M.sub.1NHAc, M.sub.1OAc, M.sub.1OBz, M.sub.1OBn, M.sub.1N.sub.3, M.sub.1OTMS, M.sub.1OTBS, ##STR00155## and M.sub.1 is selected from 0-3 methylene; or any two of R.sup.1, R.sup.2, R.sup.3, R.sup.4 are linked to form a substituted or unsubstituted ring, and each of the substituents in the ring is independently one or more selected from the group consisting of H, D, C.sub.1-8 alkyl, C.sub.1-8 alkoxyl, C.sub.2-8 alkynyl, C.sub.2-8 alkenyl, aryl, heteroaryl, halogen, cyano, carboxy, and ester group; R.sup.5 is selected from the group consisting of C.sub.1-8 alkyl, saturated cycloalkyl, saturated heterocyclyl, H, aryl, heteroaryl, C.sub.1-8 alkoxyl, halogen, cyano, carboxyl, and ester group.

3. The glycosyl donor according to claim 1, or a salt thereof, or a stereoisomer thereof, or an optical isomer thereof, wherein the structure of said glycosyl donor is selected from: ##STR00156## ##STR00157## ##STR00158##

4. The glycosyl donor according to claim 1, or a salt thereof, or a stereoisomer thereof, or an optical isomer thereof, wherein the structure of said glycosyl donor is selected from: ##STR00159## ##STR00160## ##STR00161## wherein ##STR00162## represents ##STR00163## or a mixture of thereof in any ratio.

5. A method for preparation of the glycosyl donor according to claim 1, comprising: (1) reacting a starting material Y1 with acetic anhydride to obtain compound Y2; (2) reacting compound Y2 with thiourea to obtain a reaction mixture, and adding compound Y3 to the reaction mixture for further reaction to obtain compound Y4; and (3) reacting Y4 reacts with mCPBA to obtain the glycosyl donor, wherein Y1 is ##STR00164## Y2 is ##STR00165## Y3 is ##STR00166## Y4 is ##STR00167## and X is a halogen.

6. The method according to claim 5, wherein: in step (1), a molar ratio of acetic anhydride to hydroxyl group Y1 is (0.8-1.5):1; the reaction is carried out in the presence of triethylamine and DMAP at room temperature in the solvent of dichloromethane; or in step (2), a molar ratio of Y2, thiourea, and Y3 is 1:(1.5-4.5):(1.2-2), wherein Y2 and thiourea are reacted in the presence of boron trifluoride diethyl etherate under reflux for 2-6 hours, and, after adding Y3 into the reaction mixture, the reaction is carried out in the presence of triethyl amine under reflux for 4-8 hours in the solvent of acetonitrile; or in step (3), a molar ratio of Y4 to mCPBA is 1:(1.5-4.5), and the reaction is carried out for 1-3 hours in the solvent of dichloromethane.

Description

EXAMPLES

(1) The starting materials and equipment used in the specific examples of the present invention are all known products, which are obtained by purchasing commercially available products.

(2) Synthesis of Glycosyl Donor:

(3) The following synthetic route is used to prepare the synthetic glycosyl donor of the present invention:

(4) ##STR00055##

(5) The following is a synthetic example of the allylsulfone glycosyl donor according to the present invention.

(6) 1. Synthetic Route 1

(7) 1) The Scheme of Synthetic Route

(8) ##STR00056##
2) Details of Synthetic Procedures (Taking Compound 3-1 as an Example)

(9) ##STR00057## a) Peracetyl-protected substrate 1-1 (10 mmol) was dissolved in acetonitrile (40 mL) at room temperature, to which were added thiourea (1.5 equiv.) and boron trifluoride diethyl etherate (3 equiv.), and the reaction solution was refluxed for 4 h, then cooled to room temperature. 3-Bromo-2-methylpropylene (1.5 equiv.) and triethylamine (3 equiv.) were added, and the resultant solution was refluxed for 6 h, followed by cooling to room temperature. Acetonitrile was rotatory evaporated under reduced pressure, and the residue was dissolved in dichloromethane. The solution was washed with saturated brine, extracted with dichloromethane, dried over anhydrous Na.sub.2SO.sub.4, filtered, concentrated, and separated by column chromatography (silica gel, 300-400 meshes) to obtain the corresponding thioether intermediate 2-1. b) Compound 2-1 obtained in the previous step was dissolved in dichloromethane in an ice bath, to which was slowly added m-CPBA (2.5 equiv.), and then the mixture was warmed to room temperature and reacted for 2 h. The reaction solution was filtered, and the solid was washed with dichloromethane. The filtrate was washed once with saturated Na.sub.2S.sub.2O.sub.3 solution, and washed twice with saturated Na.sub.2CO.sub.3 solution. The resultant solution was extracted with dichloromethane, dried over anhydrous Na.sub.2SO.sub.4, filtered, concentrated, and separated by column chromatography (300-400 mesh silica gel), to obtain the corresponding product, i.e. compound 3-1, with a purity of greater than 90% and a total yield of 75%.

(10) ##STR00058##

(11) Its structure was characterized by the following:

(12) .sup.1H NMR (400 MHz, Chloroform-d) 5.53 (t, J=9.6 Hz, 1H), 5.31 (t, J=9.3 Hz, 1H), 5.27 (t, J=1.6 Hz, 1H), 5.20 (d, J=1.4 Hz, 1H), 5.10 (t, J=9.8 Hz, 1H), 4.58 (d, J=9.9 Hz, 1H), 4.31-4.17 (m, 2H), 3.98 (d, J=13.6 Hz, 1H), 3.80 (ddd, J=10.1, 5.1, 2.7 Hz, 1H), 3.66 (d, J=13.6 Hz, 1H), 2.09 (s, 3H), 2.05 (s, 3H), 2.04 (s, 3H), 2.03 (s, 3H), 1.98 (s, 3H).

(13) Compounds 3-2-3-11 were synthesized by the same route as that of compound 3-1 mentioned above, and the structure and characterization data are as follows:

(14) ##STR00059##

(15) Purity >90%; total yield 62%; .sup.1H NMR (400 MHz, chloroform-d) (:=1:6) (-isomer) 5.72 (t, J=9.9 Hz, 1H), 5.47 (d, J=3.3 Hz, 1H), 5.27 (s, 1H), 5.20 (s, 1H), 5.15 (dd, J=10.1, 3.3 Hz, 1H), 4.57 (d, J=9.8 Hz, 1H), 4.19 (m, J=5.4 Hz, 2H), 4.07 (t, J=6.3 Hz, 1H), 3.99 (d, J=13.6 Hz, 1H), 3.69 (d, J=13.6 Hz, 1H), 2.19 (s, 3H), 2.06 (s, 6H), 2.00 (s, 3H), 1.98 (s, 3H).

(16) ##STR00060##

(17) Purity >90%; total yield 62%; .sup.1H NMR (400 MHz, chloroform-d) 5.94 (dd, J=3.8, 2.1 Hz, 1H), 5.59 (dd, J=9.2, 3.6 Hz, 1H), 5.29 (t, J=9.7 Hz, 1H), 5.27-5.24 (m, 1H), 5.21-5.18 (m, 1H), 4.99 (d, J=2.1 Hz, 1H), 4.70 (ddd, J=9.9, 5.8, 2.4 Hz, 1H), 4.27 (dd, J=12.5, 5.8 Hz, 1H), 4.17 (dd, J=12.5, 2.5 Hz, 1H), 4.00 (d, J=13.9 Hz, 1H), 3.67 (d, J=13.9 Hz, 1H), 2.17 (s, 3H), 2.11 (s, 3H), 2.07 (s, 3H), 2.01 (s, 3H), 1.98 (s, 3H).

(18) ##STR00061##

(19) Purity >90%; total yield 51%; .sup.1H NMR (400 MHz, chloroform-d) (:=2:1) (-isomer) 5.47 (ddd, J=9.7, 7.7, 5.1 Hz, 1H), 5.25 (s, 1H), 5.18 (s, 1H), 5.05-4.94 (m, 2H), 4.68-4.58 (m, 1H), 4.27 (dd, J=12.5, 5.6 Hz, 1H), 4.15 (dd, J=12.4, 2.5 Hz, 1H), 3.98 (d, J=13.8 Hz, 1H), 3.65 (d, J=13.8 Hz, 1H), 2.82 (ddd, J=14.8, 5.2, 3.4 Hz, 1H), 2.18-2.11 (m, 1H), 2.10 (s, 3H), 2.06 (s, 3H), 2.05 (s, 3H), 1.98 (d, J=1.4 Hz, 3H).

(20) ##STR00062##

(21) Purity >90%; total yield 35%; .sup.1H NMR (400 MHz, chloroform-d) 5.68 (t, J=9.9 Hz, 1H), 5.31 (dd, J=3.4, 1.1 Hz, 1H), 5.27 (t, J=1.5 Hz, 1H), 5.15 (s, 1H), 5.12 (dd, J=10.0, 3.4 Hz, 1H), 4.47 (d, J=9.9 Hz, 1H), 3.96-3.93 (m, 1H), 3.92 (d, J=0.9 Hz, 1H), 3.73 (d, J=13.5 Hz, 1H), 2.20 (s, 3H), 2.06 (s, 3H), 2.00 (s, 3H), 1.98 (s, 3H), 1.28 (d, J=6.4 Hz, 3H).

(22) ##STR00063##

(23) Purity >90%; total yield 58%; .sup.1H NMR (400 MHz, chloroform-d) 5.93 (dd, J=3.7, 2.0 Hz, 1H), 5.53 (dd, J=9.4, 3.7 Hz, 1H), 5.25 (p, J=1.5 Hz, 1H), 5.17 (s, 1H), 5.10 (t, J=9.5 Hz, 1H), 4.94 (d, J=2.0 Hz, 1H), 4.55 (dq, J=9.6, 6.2 Hz, 1H), 3.97 (d, J=13.9 Hz, 1H), 3.66 (d, J=13.9 Hz, 1H), 2.16 (s, 3H), 2.06 (s, 3H), 2.00 (s, 3H), 1.98 (s, 3H), 1.29 (d, J=6.2 Hz, 3H).

(24) ##STR00064##

(25) Purity >90%; total yield 63%; .sup.1H NMR (400 MHz, chloroform-d) 5.51 (t, J=9.1 Hz, 1H), 5.30 (t, J=8.9 Hz, 1H), 5.26 (t, J=1.5 Hz, 1H), 5.13 (s, 1H), 5.02 (td, J=9.0, 5.3 Hz, 1H), 4.54 (d, J=9.2 Hz, 1H), 4.39 (dd, J=11.6, 5.3 Hz, 1H), 3.91 (d, J=13.4 Hz, 1H), 3.69 (d, J=13.4 Hz, 1H), 3.47 (dd, J=11.6, 9.1 Hz, 1H), 2.10-2.00 (m, 9H), 1.97 (s, 3H).

(26) ##STR00065##

(27) Purity >90%; total yield 56%; .sup.1H NMR (400 MHz, chloroform-d) 5.75 (dd, J=7.3, 3.4 Hz, 1H), 5.49 (dd, J=5.8, 3.5 Hz, 1H), 5.26 (p, J=1.5 Hz, 1H), 5.16 (s, 1H), 5.01 (ddd, J=5.9, 4.3, 3.0 Hz, 1H), 4.76 (d, J=7.3 Hz, 1H), 4.17 (dd, J=12.4, 4.4 Hz, 1H), 4.01 (dd, J=12.4, 3.0 Hz, 1H), 3.94 (d, J=13.6 Hz, 1H), 3.69 (d, J=13.6 Hz, 1H), 2.14 (s, 1H), 2.12 (s, 3H), 2.09 (s, 3H), 1.98 (s, 3H).

(28) ##STR00066##

(29) Purity >90%; total yield 33%; .sup.1H NMR (400 MHz, chloroform-d) 5.73 (t, J=9.4 Hz, 1H), 5.35 (tt, J=2.7, 1.5 Hz, 1H), 5.27 (t, J=1.5 Hz, 1H), 5.22-5.10 (m, 1H), 4.47 (d, J=9.3 Hz, 1H), 4.24 (dd, J=12.9, 2.6 Hz, 1H), 3.92 (d, J=13.4 Hz, 1H), 3.80 (dd, J=13.0, 1.5 Hz, 1H), 3.77-3.73 (d, J=13.4 Hz, 1H), 2.18 (s, 3H), 2.08 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H).

(30) The synthetic procedures of compound 3-10 are the same as that of compound 3-1, except that 3-bromo-2-methylpropene was substituted with 3-bromopropene in the first step, with a purity of >90% and a total yield of 75%,

(31) ##STR00067##

(32) .sup.1H NMR (400 MHz, chloroform-d) 5.99-5.79 (m, 1H), 5.58-5.47 (m, 3H), 5.31 (t, J=9.3 Hz, 1H), 5.10 (t, J=9.8 Hz, 1H), 4.56 (d, J=9.9 Hz, 1H), 4.34-4.16 (m, 2H), 3.98 (dd, J=13.9, 8.4 Hz, 1H), 3.83-3.73 (m, 2H), 2.10 (s, 3H), 2.05 (s, 3H), 2.05 (s, 3H), 2.03 (s, 3H).

(33) The synthetic procedures of compound 3-11 are the same as that of compound 3-1, and only 3-bromo-2-methylpropene was substituted with 3-bromo-2-phenylpropene in the first step, with a purity of >90% and a total yield of 71%,

(34) ##STR00068##

(35) .sup.1H NMR (400 MHz, chloroform-d) 7.50-7.46 (m, 2H), 7.43-7.36 (m, 3H), 5.77 (s, 1H), 5.60 (s, 1H), 5.50 (t, J=9.6 Hz, 1H), 5.16 (t, J=9.3 Hz, 1H), 5.03 (t, J=9.8 Hz, 1H), 4.51 (d, J=14.2 Hz, 1H), 4.17 (d, J=9.9 Hz, 1H), 4.10-4.03 (m, 3H), 3.29 (dt, J=10.1, 3.5 Hz, 1H), 2.10 (s, 3H), 2.02 (s, 3H), 2.01 (s, 3H), 2.00 (s, 3H).

(36) 2. Synthetic Route 2

(37) 1) Scheme of Synthetic Route

(38) ##STR00069##
2) Details of Synthetic Procedures (Taking Compound 3-12 as an Example)

(39) ##STR00070## a) At 0 C., peracetyl-protected 2-aminoglucose substrate 1-12 (10 mmol) was dissolved in DCM (30 mL), to which was slowly added the solution of hydrobromic acid in acetic acid (33%, 30 mL) dropwise, and the mixture was stirred for 5 h. Once the starting materials disappeared, the reaction was quenched with ice water, and then the reaction solution was neutralized with the saturated aqueous solution of K.sub.2CO.sub.3 in an ice-water bath. The resultant solution was extracted with dichloromethane, and then successively washed with the ice-cold saturated aqueous solution of NaHCO.sub.3 and ice-cold saturated brine. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was rotatory evaporated, to obtain the crude product 1-12-1, that was directly used in the next step without purification; b) The crude product 1-12-1 and thiourea (1.5 equiv.) were dissolved in acetone (20 mL) and stirred under reflux at 60 C. for 10 min. A large amount of solid was precipitated. After the reaction solution was cooled to room temperature, the solid was collected by suction filtration, which was the intermediate 1-12-2. c) Intermediate 1-12-2 and anhydrous potassium carbonate (2.0 equiv.) were dissolved in acetone/water (2:1, 20 mL), and then 3-bromo-2-methylpropylene (1.5 equiv.) was added dropwise. The mixture was stirred overnight at room temperature, and the solvent was rotatory evaporated. The reaction solution was extracted with dichloromethane, successively washed with water and saturated brine. The organic phase was dried over anhydrous Na.sub.2SO.sub.4 and filtered. The filtrate was rotatory evaporated, and purified by column chromatography to obtain the thioether intermediate 2-12. d) Compound 2-12 obtained in the previous step was dissolved in dichloromethane in an ice bath, to which was slowly added m-CPBA (2.5 equiv.), and the mixture was warmed to room temperature and reacted for 2 h. The reaction solution was filtered, and the solid was washed with dichloromethane. The filtrate was successively washed once with saturated Na.sub.2S.sub.2O.sub.3 solution, and twice with saturated Na.sub.2CO.sub.3 solution. The solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography (300-400 mesh silica gel), to obtain the corresponding product compound 3-12, with a purity of greater than 90% and a total yield of 31%.

(40) Its characterization data were as follows:

(41) ##STR00071##

(42) .sup.1H NMR (400 MHz, chloroform-d) 6.07 (d, J=7.9 Hz, 1H), 5.72 (t, J=9.7 Hz, 1H), 5.25 (s, 1H), 5.21-5.15 (m, 2H), 5.05 (t, J=9.2 Hz, 1H), 4.25 (dd, J=12.6, 2.5 Hz, 1H), 4.20 (dd, J=12.6, 5.3 Hz, 1H), 4.10-4.03 (m, 1H), 4.00 (d, J=13.6 Hz, 1H), 3.89 (ddd, J=10.3, 5.2, 2.5 Hz, 1H), 3.69 (d, J=13.5 Hz, 1H), 2.09 (s, 3H), 2.05 (d, J=1.6 Hz, 6H), 1.96 (s, 3H), 1.94 (s, 3H).

(43) The synthetic route of compound 3-13 were the same as that of compound 3-12, and the product 3-13 could be obtained by using peracetyl 2-aminogalactose as the starting material. The purity was greater than 90%, and the characterization data were as follows:

(44) ##STR00072##

(45) .sup.1H NMR (400 MHz, Chloroform-d) 6.28 (d, J=8.0 Hz, 1H), 5.72 (dd, J=10.8, 3.3 Hz, 1H), 5.46 (d, J=3.3 Hz, 1H), 5.20 (s, 1H), 5.17 (d, J=10.2 Hz, 1H), 4.25 (m, 1H), 4.22-4.11 (m, 3H), 4.02 (d, J=13.5 Hz, 1H), 3.73 (d, J=13.5 Hz, 1H), 2.18 (s, 3H), 2.05 (s, 3H), 2.01 (s, 3H), 1.96 (s, 3H), 1.94 (s, 3H).

(46) 3. Synthetic Route 3

(47) 1) Scheme of Synthetic Route

(48) ##STR00073##
2) Details of Synthetic Procedures (Taking Compound 3-14 as an Example)

(49) ##STR00074## a) At 0 C., compound 1-14 (10 mmol) was dissolved in DCM (30 mL), to which were slowly added thioacetic acid (24 mmol) and boron trifluoride diethyl etherate (30 mmol), and then the mixture was warmed to room temperature and stirred overnight. Once the starting materials disappeared, the reaction was quenched with ice water. The reaction solution was extracted with dichloromethane, and then successively washed with the saturated aqueous solution of NaHCO.sub.3 and saturated brine. The organic phase was dried over anhydrous sodium sulfate, and filtered. The filtrate was rotatory evaporated, to obtain the crude product 1-14-1. b) Intermediate 1-14-1 and cysteine methyl ester hydrochloride (2.05 g, 12 mmol) were dissolved in DMF (10 mL), to which was added triethylamine (1.7 mL, 12 mmol), and the mixture was stirred at room temperature for 8 h. After the disappearance of intermediate 1-14-1 was detected by TLC, the reaction solution was extracted with ethyl acetate, and washed with half-saturated brine. The organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was rotatory evaporated, and purified by column chromatography to obtain the product Intermediate 1-14-2. c) Product intermediate 1-14-2 and anhydrous potassium carbonate (2.5 equiv.) were dissolved in acetone/water (2:1, 20 mL), and then 3-bromo-2-methylpropylene (2.5 equiv.) was added dropwise. The mixture was stirred overnight at room temperature, and the solvent was rotatory evaporated. The reaction solution was extracted with dichloromethane, successively washed with water and saturated brine. The organic phase was dried over anhydrous Na.sub.2SO.sub.4 and filtered. The filtrate was rotatory evaporated, and purified by column chromatography to obtain the thioether intermediate 2-14. d) Compound 3-12 obtained in the previous step was dissolved in dichloromethane in an ice bath, to which was slowly added m-CPBA (2.5 equiv.), and the mixture was warmed to room temperature and reacted for 2 h. The reaction solution was filtered, and the solid was washed with dichloromethane. The filtrate was successively washed once with saturated Na.sub.2S.sub.2O.sub.3 solution, and twice with saturated Na.sub.2CO.sub.3 solution. The solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography (300-400 mesh silica gel), to obtain the corresponding product compound 3-14, with a purity of greater than 90% and a total yield of 48%.

(50) Its characterization data were as follows:

(51) ##STR00075##

(52) .sup.1H NMR (400 MHz, Chloroform-d) 5.41 (d, J=4.1 Hz, 1H), 5.39-5.32 (m, 3H), 5.27 (t, J=1.5 Hz, 1H), 5.21 (s, 1H), 5.05 (t, J=9.9 Hz, 1H), 4.87 (dd, J=10.6, 4.0 Hz, 1H), 4.73-4.67 (m, 1H), 4.64 (dd, J=12.4, 2.6 Hz, 1H), 4.24 (ddd, J=24.7, 12.4, 4.6 Hz, 2H), 4.08 (dd, J=12.4, 2.3 Hz, 1H), 4.04-3.94 (m, 3H), 3.79 (ddd, J=9.7, 5.1, 2.5 Hz, 1H), 3.59 (d, J=13.7 Hz, 1H), 2.14 (s, 3H), 2.11 (s, 3H), 2.06-2.01 (m, 12H), 2.00 (s, 3H), 1.97 (s, 3H).

(53) The synthetic route of compound 3-15 were the same as that of compound 3-14, and the product 3-15 could be obtained by using peracetyl maltose as the starting material. The purity was greater than 90%, and the characterization data were as follows:

(54) ##STR00076##

(55) .sup.1H NMR (400 MHz, Chloroform-d) 5.47 (t, J=9.4 Hz, 1H), 5.38-5.35 (m, 1H), 5.32 (d, J=9.0 Hz, 1H), 5.27-5.23 (m, 1H), 5.18 (s, 1H), 5.11 (dd, J=10.5, 7.9 Hz, 1H), 4.98 (dd, J=10.4, 3.4 Hz, 1H), 4.65-4.57 (m, 2H), 4.52 (d, J=7.8 Hz, 1H), 4.18-4.04 (m, 3H), 3.97 (d, J=13.7 Hz, 1H), 3.89 (t, J=6.7 Hz, 1H), 3.82 (t, J=9.4 Hz, 1H), 3.76-3.66 (m, 1H), 3.57 (d, J=13.7 Hz, 1H), 2.15 (s, 3H), 2.12 (s, 3H), 2.07 (s, 3H), 2.06 (s, 3H), 2.05 (s, 3H), 2.04 (s, 3H), 1.97 (s, 6H).

(56) 4. Synthetic Route 4

(57) 1) Scheme of Synthetic Route

(58) ##STR00077##
2) Details of Synthetic Procedures (Taking Compound 3-16 as an Example)

(59) ##STR00078## a) At 0 C., compound 1-16 (10 mmol) was dissolved in DCM (30 mL), to which were slowly added 3-mercapto-2-methylpropylene (2.5 equiv.) and boron trifluoride diethyl etherate (30 mmol), and then the mixture was stirred 8 h at 0 C. Once the starting materials disappeared, the reaction was quenched with ice water. The reaction solution was extracted with dichloromethane, and then successively washed with the saturated aqueous solution of NaHCO.sub.3 and saturated brine. The organic phase was dried over anhydrous sodium sulfate and filtered. The filtrate was rotatory evaporated, to obtain the thioether intermediate 2-16. b) Compound 2-16 obtained in the previous step was dissolved in dichloromethane in an ice bath, to which was slowly added m-CPBA (2.5 equiv.), and the mixture was warmed to room temperature and reacted for 2 h. The reaction solution was filtered, and the solid was washed with dichloromethane. The filtrate was successively washed once with saturated Na.sub.2S.sub.2O.sub.3 solution, and twice with saturated Na.sub.2CO.sub.3 solution. The solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography (300-400 mesh silica gel), to obtain the corresponding product compound 3-16, with a purity of greater than 90% and a total yield of 48%.

(60) Its characterization data were as follows:

(61) ##STR00079##

(62) .sup.1H NMR (400 MHz, chloroform-d) 5.95-5.85 (m, 1H), 5.68 (t, J=3.2 Hz, 1H), 5.54 (dd, J=8.2, 3.2 Hz, 1H), 5.47 (t, J=6.1 Hz, 1H), 5.30-5.21 (m, 2H), 5.21-5.08 (m, 2H), 5.04 (d, J=2.6 Hz, 1H), 4.74 (m, 2H), 4.50 (dd, J=12.3, 3.4 Hz, 1H), 4.45-4.37 (m, 1H), 4.21 (m, 2H), 3.94 (m, 2H), 3.82 (dd, J=11.2, 9.0 Hz, 1H), 3.68 (d, J=13.5 Hz, 1H), 3.60 (t, J=14.7 Hz, 1H), 2.16 (s, 3H), 2.15 (s, 3H), 2.11 (s, 6H), 2.07 (s, 3H), 2.05 (s, 3H), 1.98 (s, 3H), 1.97 (s, 3H).

(63) Above-mentioned routes 1-4 could be used to synthesize substrates 3-1-3-16, and each example showed the effectiveness of these four synthetic routes.

(64) Synthesis of Compounds 3-17-3-19

(65) ##STR00080##

(66) Detailed procedures were as follows:

(67) At room temperature, the peracetyl-protected glycosyl groups synthesized by above 1-4 routes were dissolved in 10 mL methanol, and then the reaction solution was cooled to 0 C., to which was slowly added the solid of lithium hydroxide (0.5 equiv.). After addition, the temperature was still kept at 0 C., and the mixture was allowed to further react 4 h. After completion of the reaction, 2 g silica gel was directly added to the reaction solution, methanol was evaporated under reduced pressure, and the residue was purified by column chromatography, to obtain the target product. Compounds 3-17-3-19 were all prepared according to the above method, and their characterization data were as follows:

(68) ##STR00081##

(69) Purity >90%; .sup.1H NMR (400 MHz, Methanol-d.sub.4) 5.14 (m, 2H), 4.37 (d, J=9.6 Hz, 1H), 4.05 (d, J=13.6 Hz, 1H), 3.81 (dd, J=12.5, 2.1 Hz, 1H), 3.77-3.67 (m, 2H), 3.58 (dd, J=12.5, 6.2 Hz, 1H), 3.36 (t, J=8.9 Hz, 1H), 3.34-3.28 (m, 1H), 3.23-3.18 (t, J=9.4 Hz, 1H), 1.87 (s, 3H).

(70) ##STR00082##

(71) Purity >90%; .sup.1H NMR (400 MHz, deuterium oxide) 5.28-5.24 (m, 1H), 5.13 (s, 1H), 4.67 (d, J=10.3 Hz, 1H), 4.37 (t, J=10.3 Hz, 1H), 4.11 (d, J=13.7 Hz, 1H), 3.96 (d, J=3.2 Hz, 1H), 3.91 (d, J=13.7 Hz, 1H), 3.77 (m, 3H), 3.74-3.67 (m, 1H), 1.93 (s, 3H), 1.84 (s, 3H).

(72) ##STR00083##

(73) Purity >90%; .sup.1H NMR (400 MHz, deuterium oxide) 5.27 (s, 1H), 5.14 (s, 1H), 4.45 (d, J=8.0 Hz, 1H), 4.11 (d, J=14.0 Hz, 1H), 3.98-3.75 (m, 5H), 3.66 (m, 4H), 3.45-3.20 (m, 5H), 1.86 (s, 3H).

(74) Synthesis of Compound 3-20

(75) ##STR00084##

(76) Detailed procedures were as follows:

(77) At room temperature, compound 3-17, benzoyl chloride (6.0 equiv.), triethylamine (6.0 equiv.), and DMAP (0.2 equiv.) were stirred in 20 mL dichloromethane for 12 h at room temperature. After completion of the reaction, the reaction solution was extracted with 50 mL ice-cold dichloromethane. The organic layers were combined, and successively washed with the saturated aqueous solution of citric acid and saturated brine, then dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography to obtain the target product 3-20, with a purity of >90%. The characterization data are as follows:

(78) .sup.1H NMR (400 MHz, Chloroform-d) 8.04-7.99 (m, 1H), 7.97-7.86 (m, 3H), 7.85-7.80 (m, 1H), 7.61-7.27 (m, 10H), 6.07 (t, J=9.5 Hz, 1H), 5.99 (t, J=9.3 Hz, 1H), 5.69 (t, J=9.6 Hz, 1H), 5.25-5.11 (m, 2H), 4.93 (d, J=9.6 Hz, 1H), 4.73 (dd, J=12.5, 2.8 Hz, 1H), 4.53 (dd, J=12.5, 5.7 Hz, 1H), 4.28 (ddd, J=8.6, 5.5, 2.7 Hz, 1H), 4.05 (d, J=13.6 Hz, 1H), 3.71 (d, J=13.6 Hz, 1H), 1.94 (s, 3H).

(79) Synthesis of Compound 3-21

(80) ##STR00085##

(81) Detailed procedures were as follows: (1) 2,3,4,6-Tetra-O-benzyl-D-glucopyranose (i.e. 1-21, 5.4 g, 10 mmol) was dissolved in 50 mL dichloromethane, and oxalyl chloride (1.7 mL, 20 mmol) was slowly drop added to the reaction solution at 0 C., then the reaction was warmed to room temperature and stirred for 18 h. Ice water was added to quench oxalyl chloride until no gas was released. The reaction solution was extracted with dichloromethane. The organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The filtrate was rotatory evaporated, to obtain intermediate 1-21-1, that was directly used in the next step without purification. (2) Intermediate 1-21-1 and thiourea (1.2 g, 15 mmol) were dissolved in acetonitrile (30 mL), and the reaction solution was refluxed for 2 h, cooled to room temperature, to which were then added triethylamine (15 mmol), 3-bromo-2-methylpropylene (15 mmol). After refluxing for 4 h, the reaction solution was cooled to room temperature. Acetonitrile was rotatory evaporated under reduced pressure, and to the residue were added dichloromethane and water. The resultant solution was extracted with dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The filtrate was concentrated, to obtain corresponding intermediate 2-21, that was directly used in the next step without purification. (3) At 0 C., crude intermediate 2-21 obtained in the previous step was dissolved in dichloromethane (10 mL), to which was slowly added m-CPBA (2.5 equiv.), and the reaction was further stirred for 2 h. After intermediate 2-21 disappeared by TLC detection, the reaction solution was filtered, and the filtrate was successively washed with saturated NaHCO.sub.3 aqueous solution and saturated brine. The organic phase was dried over anhydrous sodium sulfate and filtered. The filtrate was rotatory evaporated and purified by column chromatography, to obtain the product 3-21 (4.5 g, with a purity of >90% and a three-step total yield of 70%) (i.e. compound 3-21).

(82) ##STR00086##

(83) .sup.1H NMR (CDCl.sub.3, 400 MHz) : 7.44-7.22 (m, 18H), 7.16 (dd, J=6.1, 3.1 Hz, 2H), 5.21 (s, 0.32H), 5.16 (d, J=1.6 Hz, 1H), 5.09 (s, 0.68H), 5.04 (d, J=6.0 Hz, 0.69H), 4.99 (d, J=9.7 Hz, 0.33H), 4.94 (d, J=11.1 Hz, 0.34H), 4.90-4.66 (m, 4.6H), 4.58-4.38 (m, 4.0H), 4.15-4.06 (m, 1H), 4.04 (d, J=13.7 Hz, 0.34H), 3.94 (d, J=13.5 Hz, 0.69H), 3.80-3.74 (m, 0.35H), 3.74-3.50 (m, 4.6H), 1.96 (s, 1H), 1.94 (s, 2H).

(84) Synthesis of Compounds 3-22-3-38

(85) ##STR00087##

(86) Detailed procedures were as follows: a) At room temperature, the peracetyl-protected thioether substrates synthesized by above 1-4 routes were dissolved in 10 mL methanol, and then the reaction solution was cooled to 0 C., to which was slowly added the solid of lithium hydroxide (0.5 equiv.). After addition, the temperature was still kept at 0 C., and the mixture was allowed to react 1 h. After completion of the reaction, the reaction solution was rotatory evaporated, and the crude product was dissolved in DMF (10 mL). 60% NaH (OH/1.5 equiv.) was slowly added in batches at 0 C., and the mixture was stirred for 30 min, to which was then added benzyl bromide (OH/1.5 equiv.). The reaction was further stirred for 30 min, and then warmed to room temperature, followed by stirring for additional 12 h. After completion of the reaction, ice water was added, and the resultant solution was extracted with dichloromethane. The organic layers were combined, successively washed with water and saturated brine, dried with anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography, to obtain a perbenzyl-protected thioether intermediate. b) At 0 C., the intermediate obtained in the previous step was dissolved in dichloromethane (10 mL), to which was slowly added m-CPBA (2.5 equiv.), and the reaction was further stirred for 2 h. After the starting material disappeared by TLC detection, the reaction solution was filtered, and the filtrate was successively washed with saturated NaHCO.sub.3 aqueous solution and saturated brine. The organic phase was dried over anhydrous sodium sulfate and filtered. The filtrate was rotatory evaporated and purified by column chromatography, to obtain the products 3-22-3-38.

(87) The characterization data were as follows.

(88) ##STR00088##

(89) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.42-7.20 (m, 20H), 5.14 (d, J=1.6 Hz, 2H), 4.96 (d, J=11.5 Hz, 2H), 4.82 (d, J=9.7 Hz, 1H), 4.74 (d, J=2.6 Hz, 2H), 4.61 (d, J=11.7 Hz, 1H), 4.48-4.38 (m, 4H), 3.97 (d, J=13.7 Hz, 1H), 3.88 (d, J=2.7 Hz, 1H), 3.68-3.56 (m, 4H), 3.49 (dd, J=7.9, 4.4 Hz, 1H), 1.95 (d, J=1.3 Hz, 3H).

(90) ##STR00089##

(91) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.43-7.24 (m, 15H), 5.17 (t, J=1.6 Hz, 1H), 5.08 (s, 1H), 5.01 (d, J=11.7 Hz, 1H), 4.97 (d, J=9.7 Hz, 1H), 4.83 (d, J=9.7 Hz, 1H), 4.78 (d, J=11.9 Hz, 1H), 4.74 (d, J=11.8 Hz, 1H), 4.70 (d, J=11.7 Hz, 1H), 4.49-4.38 (m, 2H), 3.96 (d, J=13.6 Hz, 1H), 3.69-3.51 (m, 4H), 1.96 (d, J=1.1 Hz, 3H), 1.24 (d, J=6.4 Hz, 3H).

(92) ##STR00090##

(93) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.39-7.24 (m, 15H), 5.17 (t, J=1.6 Hz, 1H), 5.11 (s, 1H), 4.92 (d, J=2.4 Hz, 1H), 4.84 (d, J=11.2 Hz, 1H), 4.69 (d, J=11.9 Hz, 1H), 4.63 (dd, J=12.2, 6.0 Hz, 3H), 4.56 (d, J=11.1 Hz, 1H), 4.44 (t, J=2.9 Hz, 1H), 4.35-4.26 (m, 1H), 4.08 (dd, J=8.4, 3.4 Hz, 1H), 3.90 (d, J=13.8 Hz, 1H), 3.60 (t, J=8.8 Hz, 1H), 3.54 (d, J=13.8 Hz, 1H), 1.92 (s, 3H), 1.31 (d, J=6.2 Hz, 3H).

(94) ##STR00091##

(95) 7.40-7.24 (m, 15H), 5.20 (t, J=1.6 Hz, 1H), 5.08 (s, 1H), 4.94-4.90 (m, 1H), 4.90-4.84 (m, 2H), 4.78 (d, J=9.8 Hz, 1H), 4.69 (d, J=11.7 Hz, 1H), 4.59 (d, J=11.6 Hz, 1H), 4.46 (d, J=9.2 Hz, 1H), 4.11 (dd, J=11.4, 5.0 Hz, 1H), 4.05 (t, J=8.8 Hz, 1H), 3.89 (d, J=13.6 Hz, 1H), 3.76-3.64 (m, 2H), 3.61 (d, J=13.5 Hz, 1H), 3.30 (dd, J=11.5, 9.1 Hz, 1H), 1.95 (s, 3H).

(96) ##STR00092##

(97) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.39-7.19 (m, 15H), 5.17 (t, J=1.7 Hz, 1H), 5.09 (s, 1H), 4.85 (d, J=6.8 Hz, 1H), 4.67 (dd, J=11.7, 3.5 Hz, 2H), 4.58 (dd, J=11.7, 5.8 Hz, 2H), 4.50 (d, J=3.1 Hz, 2H), 4.35 (dd, J=6.8, 3.0 Hz, 1H), 4.02 (dd, J=11.9, 4.3 Hz, 1H), 3.93-3.83 (m, 3H), 3.67-3.63 (m, 1H), 3.61 (d, J=13.7 Hz, 1H), 1.94 (s, 3H).

(98) ##STR00093##

(99) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.42-7.26 (m, 15H), 5.18 (q, J=1.6 Hz, 1H), 5.08 (s, 1H), 4.90 (d, J=10.0 Hz, 1H), 4.85 (d, J=10.0 Hz, 1H), 4.75 (d, J=12.5 Hz, 1H), 4.71-4.59 (m, 3H), 4.51-4.38 (m, 2H), 4.23 (dd, J=12.4, 3.0 Hz, 1H), 3.91 (d, J=13.6 Hz, 1H), 3.76 (td, J=3.0, 1.4 Hz, 1H), 3.71-3.61 (m, 2H), 3.38 (dd, J=12.5, 1.5 Hz, 1H), 1.96 (s, 3H).

(100) ##STR00094##

(101) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.34-7.12 (m, 35H), 5.51 (d, J=3.7 Hz, 1H), 5.17 (s, 2H), 4.95-4.72 (m, 6H), 4.64-4.34 (m, 9H), 4.16 (t, J=8.8 Hz, 1H), 4.09-3.97 (m, 2H), 3.87 (t, J=9.4 Hz, 2H), 3.80-3.68 (m, 3H), 3.68-3.52 (m, 4H), 3.48 (dt, J=10.5, 3.1 Hz, 2H), 1.96 (s, 3H).

(102) ##STR00095##

(103) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.37-7.22 (m, 15H), 5.18 (ddt, J=7.4, 5.7, 2.9 Hz, 1H), 4.90 (t, J=10.1 Hz, 1H), 4.81-4.37 (m, 7H), 4.26-4.11 (m, 1H), 3.99 (dd, J=26.0, 13.7 Hz, 1H), 3.78-3.53 (m, 4H), 3.53-3.45 (m, 1H), 1.94 (s, 3H).

(104) ##STR00096##

(105) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.37-7.26 (m, 13H), 7.19 (dd, J=7.3, 2.3 Hz, 2H), 5.77 (d, J=7.0 Hz, 1H), 5.22-5.10 (m, 3H), 4.85 (d, J=11.5 Hz, 1H), 4.81 (d, J=11.0 Hz, 1H), 4.68 (d, J=11.5 Hz, 1H), 4.57 (d, J=10.8 Hz, 1H), 4.55-4.46 (m, 3H), 3.97 (d, J=13.6 Hz, 1H), 3.79-3.43 (m, 7H), 1.92 (s, 3H), 1.85 (s, 3H).

(106) ##STR00097##

(107) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.44-7.26 (m, 13H), 7.16 (dd, J=7.3, 2.3 Hz, 2H), 5.26-5.20 (m, 1H), 5.17 (s, 1H), 4.91 (d, J=1.8 Hz, 1H), 4.81 (d, J=11.1 Hz, 1H), 4.75 (s, 2H), 4.58 (d, J=12.1 Hz, 1H), 4.51-4.45 (m, 3H), 4.42 (ddd, J=9.8, 5.1, 2.3 Hz, 1H), 4.34 (dd, J=8.7, 3.9 Hz, 1H), 3.97 (d, J=13.9 Hz, 1H), 3.85 (t, J=9.2 Hz, 1H), 3.69-3.54 (m, 3H), 1.94 (s, 3H).

(108) ##STR00098##

(109) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.42-7.24 (m, 48H), 7.16 (dd, J=7.0, 2.5 Hz, 6H), 5.98-5.80 (m, 3H), 5.51-5.33 (m, 6H), 5.00 (d, J=6.3 Hz, 2H), 4.96 (d, J=6.5 Hz, 1H), 4.92 (d, J=7.9 Hz, 1H), 4.87 (d, J=4.2 Hz, 2H), 4.83 (d, J=9.0 Hz, 2H), 4.78 (d, J=8.3 Hz, 3H), 4.76-4.73 (m, 2H), 4.70 (d, J=11.5 Hz, 2H), 4.55 (d, J=11.6 Hz, 3H), 4.51 (d, J=11.8 Hz, 3H), 4.48 (d, J=9.1 Hz, 2H), 4.46-4.43 (m, 2H), 4.43-4.36 (m, 3H), 4.13-4.05 (m, 3H), 3.98 (dt, J=13.9, 8.8 Hz, 3H), 3.77 (t, J=8.5 Hz, 1H), 3.74-3.48 (m, 12H).

(110) ##STR00099##

(111) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.33-7.19 (m, 15H), 5.17 (s, 1H), 5.14 (t, J=1.6 Hz, 1H), 4.94 (d, J=9.7 Hz, 1H), 4.89 (d, J=11.0 Hz, 1H), 4.82 (d, J=11.0 Hz, 1H), 4.78 (d, J=11.0 Hz, 1H), 4.71 (d, J=9.7 Hz, 1H), 4.59 (d, J=11.0 Hz, 1H), 4.45 (d, J=9.5 Hz, 1H), 4.07-3.95 (m, 2H), 3.83-3.66 (m, 3H), 3.58-3.47 (m, 2H), 3.34 (ddd, J=9.7, 5.1, 1.8 Hz, 1H), 1.93 (d, J=1.2 Hz, 3H), 0.84 (s, 9H), 0.02 (s, 3H), 0.00 (s, 3H).

(112) ##STR00100##

(113) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.32-7.28 (m, 13H), 7.17 (dt, J=7.2, 2.4 Hz, 2H), 5.00 (d, J=9.7 Hz, 1H), 4.97 (d, J=11.1 Hz, 1H), 4.89 (d, J=10.7 Hz, 1H), 4.85 (d, J=7.8 Hz, 1H), 4.84 (s, 1H), 4.74 (d, J=9.7 Hz, 1H), 4.59 (d, J=10.8 Hz, 1H), 4.48 (dd, J=12.1, 1.7 Hz, 1H), 4.03-3.97 (m, 1H), 3.79 (t, J=8.6 Hz, 1H), 3.70-3.63 (m, 2H), 3.60-3.51 (m, 4H), 2.04 (s, 3H), 1.98 (s, 3H).

(114) ##STR00101##

(115) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.58-7.27 (m, 15H), 5.59 (s, 1H), 5.22 (s, 1H), 5.07 (s, 1H), 5.02-4.75 (m, 4H), 4.58 (d, J=9.4 Hz, 1H), 4.37 (dd, J=10.5, 5.0 Hz, 1H), 4.16 (t, J=8.9 Hz, 1H), 3.96-3.81 (m, 3H), 3.77 (t, J=9.4 Hz, 1H), 3.66 (d, J=13.6 Hz, 1H), 3.52 (dt, J=9.8, 4.9 Hz, 1H), 1.97 (s, 3H).

(116) ##STR00102##

(117) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.47-7.41 (m, 2H), 7.39-7.27 (m, 8H), 5.14 (p, J=1.5 Hz, 1H), 4.99-4.90 (m, 2H), 4.84 (d, J=10.5 Hz, 1H), 4.77 (d, J=10.5 Hz, 1H), 4.64 (d, J=11.9 Hz, 1H), 4.53-4.44 (m, 2H), 4.38 (dq, J=9.0, 6.1 Hz, 1H), 3.89 (d, J=13.0 Hz, 1H), 3.71 (d, J=12.8 Hz, 1H), 3.52 (dd, J=8.9, 4.3 Hz, 1H), 1.89 (t, J=1.2 Hz, 3H), 1.32 (d, J=6.1 Hz, 3H).

(118) ##STR00103##

(119) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.41-7.17 (m, 15H), 5.23 (t, J=1.6 Hz, 1H), 5.18 (s, 1H), 4.96 (d, J=3.6 Hz, 1H), 4.74 (dd, J=4.8, 3.7 Hz, 1H), 4.70 (d, J=11.7 Hz, 1H), 4.59-4.43 (m, 6H), 4.22 (dd, J=8.5, 4.8 Hz, 1H), 3.96 (d, J=13.7 Hz, 1H), 3.75-3.62 (m, 2H), 3.56 (dd, J=11.5, 4.5 Hz, 1H), 1.99 (s, 3H).

(120) ##STR00104##

(121) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 7.39-7.24 (m, 15H), 5.20 (t, J=1.6 Hz, 1H), 5.15 (s, 1H), 5.02 (d, J=1.5 Hz, 1H), 4.68 (d, J=11.8 Hz, 1H), 4.61-4.42 (m, 6H), 4.39 (d, J=11.6 Hz, 1H), 4.02 (dd, J=8.2, 5.2 Hz, 1H), 3.87 (d, J=13.8 Hz, 1H), 3.69 (dd, J=11.0, 3.1 Hz, 1H), 3.61 (dd, J=11.0, 6.5 Hz, 1H), 3.52 (d, J=13.7 Hz, 1H), 1.94 (s, 3H).

(122) The synthesis of compounds 3-39-3-40 was performed by the same route as that of compound 3-1 above, and their structures and characterization data were as follows:

(123) ##STR00105##

(124) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 5.96 (ddt, J=16.6, 10.0, 5.9 Hz, 1H), 5.32 (dd, J=17.2, 1.7 Hz, 1H), 5.24-5.18 (m, 2H), 5.13 (s, 1H), 4.44 (d, J=7.9 Hz, 1H), 4.37-4.22 (m, 4H), 4.17 (dd, J=12.6, 4.3 Hz, 1H), 4.11 (dd, J=8.0, 6.1 Hz, 1H), 3.95 (d, J=13.6 Hz, 1H), 3.89 (dd, J=12.5, 4.0 Hz, 1H), 3.67 (d, J=13.6 Hz, 1H), 1.98 (d, J=1.4 Hz, 3H), 1.54 (s, 3H), 1.37 (s, 3H).

(125) ##STR00106##

(2R,3R,4S,5R)-2-(acetoxymethyl)-6-((2-methylenedecyl)sulfonyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate

(126) Purity >90%; .sup.1H NMR (400 MHz, chloroform-d) 5.53 (t, J=9.6 Hz, 1H), 5.31 (t, J=9.4 Hz, 1H), 5.28-5.19 (m, 2H), 5.10 (t, J=9.8 Hz, 1H), 4.57 (d, J=10.0 Hz, 1H), 4.25 (dd, J=5.4, 3.8 Hz, 2H), 3.95 (d, J=13.6 Hz, 1H), 3.80 (dq, J=7.4, 2.5 Hz, 1H), 3.68 (d, J=13.6 Hz, 1H), 2.26 (t, J=7.7 Hz, 2H), 2.19-1.95 (m, 12H), 1.46 (dt, J=14.7, 7.2 Hz, 2H), 1.38-1.15 (m, 10H), 0.88 (t, J=6.6 Hz, 3H). .sup.13C NMR (101 MHz, chloroform-d) 170.37, 170.09, 169.20, 169.13, 136.99, 119.74, 85.59, 73.16, 67.54, 66.11, 61.64, 55.84, 35.73, 31.85, 29.41, 29.23, 29.09, 27.33, 22.65, 20.68, 20.60, 20.54, 20.52, 14.10.

(127) Synthesis of S-Glycosyl Compound:

(128) Then, the allylsulfone glycosyl donor prepared above was used as raw material to react with the glycosyl acceptor, to synthesize S-glycosyl compound of the present invention. For example, using the above compound 3-1 as a raw material, the synthetic route was as follows: Route 1: Under nitrogen atmosphere, compound 3-1 (1.0 equiv), glycosyl acceptor a (1.2 equiv), and photosensitizer Ir[dF(CF.sub.3)(ppy).sub.2](dtbbpy)PF.sub.6 (0.01 equiv) were added to the flask for catalytic reaction, to which was added acetonitrile (making the concentration of compound 3-1 be 0.1 mol/L), and the reaction was stirred at room temperature for 4 h under the irradiation of Blue LED, to obtain the S-glycosyl compound S-a.

(129) ##STR00107##

(130) Wherein, Y is selected from NH or O; R.sup.1 is selected from methyl,

(131) ##STR00108##
R.sup.2 is selected from Bz, H,

(132) ##STR00109##
and Boc. Route 2: Under nitrogen atmosphere, compound 3-1 (1.0 equiv), disulfide compound b (2.0 equiv), and photosensitizer Ir[dF(CF.sub.3)(ppy).sub.2](dtbbpy)PF.sub.6 (0.01 equiv) were added to the flask for catalytic reaction, to which was added acetonitrile (making the concentration of compound 3-1 be 0.1 mol/L), and the reaction was stirred at 45 C. for 2 h under the irradiation of Blue LED, to obtain the S-glycosyl compound S-b.

(133) ##STR00110##

(134) Wherein, Ar represents aryl. Route 3: Under nitrogen atmosphere, compound 3-1 (1.0 equiv.), disulfide compound c (2.0 equiv.), and photosensitizer Ir[dF(CF.sub.3)(ppy).sub.2](dtbbpy)PF.sub.6 (0.01 equiv.) were added to the flask for catalytic reaction, to which was added acetonitrile (0.1 mol/L), and the reaction was stirred at room temperature for 2 h under the irradiation of Blue LED, to obtain the S-glycosyl compound S-c.

(135) ##STR00111##

(136) Wherein, Alkyl represents alkyl. Route 4: Under nitrogen atmosphere, compound 3-x (1.0 equiv), glycosyl disulfide receptor d (1.2 equiv), and photosensitizer Ir[dF(CF.sub.3)(ppy).sub.2](dtbbpy)PF.sub.6 (0.01 equiv) were added to the flask for catalytic reaction, to which was added acetonitrile (making the concentration of compound 3-1 to be 0.1 mol/L), and the reaction was stirred at room temperature for 4 h under the irradiation of Blue LED, to obtain the S-glycosyl compound S-d.

(137) ##STR00112##

(138) The above synthetic route of the present invention was not limited to using compound 3-1 as a raw material. Using the same method, replacing the raw material compound 3-1 with any allylsulfone glycosyl donor prepared above in the present invention could obtain the corresponding S-glycosyl compounds.

(139) The following are synthetic examples of specific S-glycosyl compounds according to the present invention.

Example 17 Synthesis of S-Glycoside Compound S-1-S-17 and S-22 According to the Present Invention

(140) Using the same method as that of route 1 above, S-glycosyl compounds S-1-S-17 and S-22 according to the present invention were prepared. The structure and characterization are as follows:

(141) ##STR00113##

(142) Methyl N-benzoyl-S-(2,3,4,6-tetraacetoxy-1--D-glucosyl)-L-cysteine (with a purity of >90%, yield=92%)

(143) .sup.1H NMR (400 MHz, chloroform-d) 7.83 (m, 2H), 7.58-7.49 (m, 1H), 7.43 (m, 3H), 5.64 (d, J=5.8 Hz, 1H), 5.32-5.20 (m, 2H), 5.07-4.94 (m, 2H), 4.37 (ddd, J=10.3, 5.0, 2.2 Hz, 1H), 4.25 (dd, J=12.6, 5.0 Hz, 1H), 4.16 (dd, J=10.6, 2.2 Hz, 1H), 3.80 (s, 2H), 3.35 (dd, J=14.6 Hz, J=3.5 Hz, 1H), 3.13 (dd, J=14.6, 3.5 Hz, 1H), 2.07 (s, 3H), 2.02 (s, 3H), 2.02 (s, 3H), 1.99 (s, 3H).

(144) ##STR00114##

(145) Methyl N-benzoyl-S-(2,3,4,6-tetraacetoxy-2-deoxyamino--D-glucosyl)-L-cysteine (with a purity of >90%, Yield=70%)

(146) .sup.1H NMR (400 MHz, chloroform-d) 7.89-7.84 (m, 2H), 7.57-7.50 (m, 2H), 7.43 (m, 2H), 5.80 (d, J=8.8 Hz, 1H), 5.41 (d, J=5.3 Hz, 1H), 5.35-5.29 (m, 1H), 5.14-5.07 (t, J=9.6 Hz, 1H), 4.98 (dd, J=11.3, 9.3 Hz, 1H), 4.54 (ddd, J=11.3, 8.8, 5.3 Hz, 1H), 4.32 (dt, J=10.1, 3.6 Hz, 1H), 4.20 (d, J=3.7 Hz, 2H), 3.80 (s, 3H), 3.41 (dd, J=14.7, 4.7 Hz, 1H), 3.17 (dd, J=14.6, 3.3 Hz, 1H), 2.04 (s, 3H), 2.03 (s, 3H), 1.97 (s, 3H), 1.96 (s, 3H).

(147) ##STR00115##

(148) Methyl N-benzoyl-S-(2,3,4,6-tetraacetoxy-1--D-mannosyl)-L-cysteine (with a purity of >90%, Yield=88%)

(149) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.85 (m, 2H), 7.57-7.50 (m, 1H), 7.43 (m, 2H), 5.38 (dd, J=3.3, 1.7 Hz, 1H), 5.32-5.24 (m, 3H), 5.18 (dd, J=10.0, 3.3 Hz, 1H), 4.33 (d, J=4.4 Hz, 1H), 4.26-4.15 (m, 2H), 3.80 (s, 3H), 3.38 (dd, J=14.5, 4.9 Hz, 1H), 3.22 (dd, J=14.5, 3.6 Hz, 1H), 2.14 (s, 3H), 2.05 (s, 3H), 1.99 (s, 3H), 1.95 (s, 3H).

(150) ##STR00116##

(151) Methyl N-benzoyl-S-(2,3,4-triacetoxy-1--D-rhamnosyl)-L-cysteine (with a purity of >90%, Yield=87%)

(152) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.50 (m, 1H), 7.43 (m, 2H), 5.34 (dd, J=3.4, 1.6 Hz, 1H), 5.22 (d, J=1.6 Hz, 1H), 5.18 (dd, J=10.0, 3.4 Hz, 1H), 5.11-5.04 (m, 2H), 4.21-4.07 (m, 1H), 3.35 (dd, J=13.9, 5.0 Hz, 1H), 3.16 (dd, J=13.9, 4.9 Hz, 1H), 2.09 (s, 3H), 2.05 (s, 3H), 1.97 (s, 3H), 1.23 (d, J=6.2 Hz, 3H).

(153) ##STR00117##

(154) Methyl N-benzoyl-S-(3,4,6-triacetoxy-2-deoxy--D-glucosyl)-L-cysteine (with a purity of >90%, Yield=72%)

(155) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.50 (m, 1H), 7.43 (m, 2H), 5.43-5.39 (m, d, J=5.1 Hz, 1H), 5.29-5.23 (m, 1H), 5.21-5.13 (m, 1H), 4.96 (t, J=9.6 Hz, 1H), 4.33 (ddd, J=9.8, 5.3, 2.0 Hz, 1H), 4.27 (dd, J=12.3, 5.3 Hz, 1H), 4.13 (dd, J=12.3, 2.0 Hz, 1H), 3.79 (s, 3H), 3.35 (dd, J=14.6, 5.0 Hz, 1H), 3.16 (dd, J=14.6, 3.6 Hz, 1H), 2.35 (ddd, J=13.4, 5.2, 1.4 Hz, 1H), 2.25-2.14 (m, 1H), 2.04 (s, 3H), 2.00 (s, 3H), 1.97 (s, 3H).

(156) ##STR00118##

(157) Methyl N-benzoyl-S-(2,3,6,2,3,4,6-heptaacetoxy--D-maltosyl)-L-cysteine (with a purity of >90%, Yield=75%)

(158) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.50 (m, 1H), 7.43 (m, 2H), 5.50 (d, J 5.7 Hz, JH), 5.42-5.32 (m, 2H), 5.30-5.21 (m, 2H), 5.12-5.04 (t, J=9.8 Hz, 1H), 4.91 (m, 2H), 4.51 (d, J=2.3 Hz, 1H), 4.31 (ddd, J=9.8, 5.2, 2.2 Hz, 1H), 4.24 (dd, J=12.4, 3.8 Hz, 1H), 4.15 (dd, J=12.3, 5.3 Hz, 1H), 4.07 (dd, J=12.5, 2.4 Hz, 1H), 4.03-3.97 (m, 1H), 3.87 (dd, J=9.8, 7.9 Hz, 1H), 3.83 (s, 3H), 3.34 (dd, J=14.6, 4.7 Hz, 1H), 3.16 (dd, J=14.6, 3.6 Hz, 1H), 2.10 (s, 3H), 2.06 (s, 3H), 2.05 (s, 2H), 2.04 (s, 3H), 2.03 (s, 3H), 2.01 (s, 2H), 2.00 (s, 3H).

(159) ##STR00119##

(160) Methyl N-benzoyl-S-(2,3,6,2,3,4,6-heptaacetoxy--D Lactosyl)-L-cysteine (with a purity of >90%, Yield=80%)

(161) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.51 (m, 1H), 7.42 (m, 2H), 5.56 (d, J=5.7 Hz, 1H), 5.35 (d, J=3.4 Hz, 1H), 5.27 (t, J=9.5 Hz, 1H), 5.22 (m, 1H), 5.10 (dd, J=10.4, 7.9 Hz, 1H), 4.99-4.93 (m, 2H), 4.54-4.47 (m, 2H), 4.27 (ddd, J=10.1, 5.4, 1.9 Hz, 1H), 4.18-4.05 (m, 3H), 3.89 (t, J=6.9 Hz, 1H), 3.78 (s, 3H), 3.75-3.70 (t, J=9.4 Hz, 1H), 3.30 (dd, J=14.5, 5.0 Hz, 1H), 3.11 (dd, J=14.5, 3.6 Hz, 1H), 2.14 (s, 3H), 2.06 (s, 3H), 2.05 (s, 6H), 2.04 (s, 3H), 2.01 (s, 3H), 1.96 (s, 3H).

(162) ##STR00120##

(163) Methyl N-benzoyl-S-(2,3,4-triacetoxy--L-lyxosyl)-L-cysteine (with a purity of >90%, Yield=63%)

(164) .sup.1H NMR (400 MHz, Chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.51 (m, 1H), 7.42 (m, 2H), 5.29 (dd, J=4.5, 3.3 Hz, 1H), 5.22 (dd, J=8.1, 3.3 Hz, 1H), 5.15 (dt, J=8.3, 4.3 Hz, 1H), 5.13-5.06 (m, 1H), 5.05-5.02 (m, 1H), 3.86 (d, J=2.3 Hz, 1H), 3.80 (s, 3H), 3.79 (d, J=2.8 Hz, 1H), 3.41 (dd, J=14.5, 4.7 Hz, 1H), 3.15 (dd, J=14.5, 3.9 Hz, 1H), 2.09 (s, 3H), 2.07 (s, 3H), 2.04 (s, 3H).

(165) ##STR00121##

(166) Methyl N-benzoyl-S-(2,3,4-triacetoxy--D-arabinosyl)-L-cysteine (with a purity of >90%, Yield=76%)

(167) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.51 (m, 1H), 7.42 (m, 2H), 5.72 (d, J=5.3 Hz, 1H), 5.30-5.27 (m, 1H), 5.23 (dd, J=10.1, 5.1 Hz, 1H), 5.17-5.13 (m, 1H), 5.08-5.03 (m, 1H), 4.21-4.15 (dd, J=13.2, 1.5 Hz, 1H), 3.80 (s, 3H), 3.35 (dd, J=14.1, 4.6 Hz, 1H), 3.05 (dd, J=14.1, 5.3 Hz, 1H), 2.11 (s, 3H), 2.05 (s, 2H), 2.00 (s, 3H).

(168) ##STR00122##

(169) Methyl N-benzoyl-S-(2,3,5-triacetoxy--D-ribosyl)-L-cysteine (with a purity of >90%, Yield=78%)

(170) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.51 (m, 1H), 7.42 (m, 2H), 5.48 (t, J=3.2 Hz, 1H), 4.92 (d, J=7.7 Hz, 1H), 5.02 (m, 3H), 3.97 (dd, J=11.6, 4.4 Hz, 1H), 3.80 (s, 3H), 3.71 (dd, J=11.6, 8.3 Hz, 1H), 3.34 (dd, J=14.3, 4.7 Hz, 1H), 3.20 (dd, J=14.3, 5.3 Hz, 1H), 2.05 (s, 3H), 2.04 (s, 3H), 2.03 (s, 3H).

(171) ##STR00123##

(172) Methyl N-benzoyl-S-(2,3,4,6-tetraacetoxy--D-galactosyl)-L-cysteine (with a purity of >90%, Yield=63%)

(173) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.51 (m, 1H), 7.42 (m, 2H), 5.72 (d, J=5.6 Hz, 1H), 5.44 (d, J=3.3, 1H), 5.27 (dd, J=11.1, 5.6 Hz, 1H), 5.20 (m, 1H), 5.14 (dd, J=11.0, 3.3 Hz, 1H), 4.56 (t, J=6.4 Hz, 1H), 4.17 (dd, J=11.4, 5.2 Hz, 1H), 4.03 (dd, J=11.4, 7.4 Hz, 1H), 3.80 (s, 3H), 3.34 (dd, J=14.5, 4.9 Hz, 1H), 3.13 (dd, J=14.4, 3.8 Hz, 1H), 2.15 (s, 3H), 2.07 (s, 3H), 1.99 (s, 3H), 1.91 (s, 3H).

(174) ##STR00124##

(175) Methyl N-benzoyl-S-(2,3,4-triacetoxy--L-fucosyl)-L-cysteine (with a purity of >90%, Yield=71%)

(176) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.57-7.51 (m, 1H), 7.42 (m, 2H), 5.82 (d, J=5.1 Hz, 1H), 5.26 (m, 1H), 5.22-5.16 (m, 2H), 5.08 (m, 1H), 4.40 (q, J=6.5 Hz, 1H), 3.81 (s, 3H), 3.28 (dd, J=14.0, 4.6 Hz, 1H), 3.05 (dd, J=14.0, 5.2 Hz, 1H), 2.15 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H), 1.15 (d, J=6.5 Hz, 3H).

(177) ##STR00125##

(178) Methyl N-benzoyl-S-(2,3,4-triacetoxy--L-xylosyl)-L-cysteine (with a purity of >90%, Yield=73%)

(179) .sup.1H NMR (400 MHz, chloroform-d) 5.50 (d, J=5.3 Hz, 1H), 5.23 (t, J=9.2 Hz, 1H), 5.17 (m, 1H), 5.05 (m, 1H), 4.99-4.87 (m, 4H), 4.54 (d, J=9.2 Hz, 1H), 4.10 (dd, J=11.6, 5.3 Hz, 1H), 3.98-3.89 (m, 1H), 3.80 (s, 3H), 3.38 (s, 3H), 3.38-3.30 (m, 2H), 3.20 (dd, J=14.4, 5.3 Hz, 1H), 3.11 (dd, J=14.5, 3.8 Hz, 1H), 2.07 (s, 3H), 2.04 (s, 3H), 2.03 (s, 6H), 1.99 (s, 6H).

(180) ##STR00126##

(181) Methyl N(N-t-butoxy-L-valinyl)-S-(2,3,4,6-tetraacetoxy-D-glucosyl)-L-cysteine (with a purity of >90%, Yield=70%)

(182) .sup.1H NMR (400 MHz, chloroform-d) 5.60 (d, J=5.8 Hz, 1H), 5.25 (d, J=9.8 Hz, 1H), 5.17-5.07 (m, 1H), 5.02-4.96 (m, 1H), 4.91 (m, 1H), 4.35-4.28 (m, 2H), 4.26-4.20 (m, 1H), 4.01 (m, 1H), 3.78 (s, 3H), 3.16-3.03 (m, 2H), 2.22-2.15 (m, 1H), 2.11 (s, 3H), 2.06 (s, 2H), 2.04 (s, 3H), 2.01 (s, 3H), 1.46 (s, 9H), 1.00-0.97 (d, J=6.9 Hz, 3H), 0.93 (d, J=6.9 Hz, 3H).

(183) ##STR00127##

(184) Methyl N(N-t-butoxy-L-threoninyl)-S-(2,3,4,6-tetraacetoxy-D-glucosyl)-L-cysteine (with a purity of >90%, Yield=90%)

(185) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.65 (t, J=7.4 Hz, 1H), 7.59-7.52 (m, 2H), 7.48 (d, J=7.9 Hz, 1H), 5.67 (d, J=5.7 Hz, 1H), 5.54 (d, J=7.7 Hz, 1H), 5.27 (t, J=9.8 Hz, 1H), 5.08-5.01 (m, 1H), 4.96 (dd, J=10.4, 5.8 Hz, 1H), 4.94-4.88 (m, 1H), 4.40 (dd, J=6.6, 2.4 Hz, 1H), 4.33 (dt, J=10.1, 3.6 Hz, 1H), 4.25 (d, J=2.6 Hz, 2H), 4.19-4.14 (m, 1H), 3.76 (s, 3H), 3.08 (d, J=4.8 Hz, 2H), 2.12 (s, 3H), 2.06 (s, 3H), 2.04 (s, 3H), 2.01 (s, 3H), 1.48 (s, 9H), 1.21 (d, J=6.3 Hz, 3H).

(186) ##STR00128##

(187) Methyl N(N-t-butoxy-L-tyrosinyl)-S-(2,3,4,6-tetraacetoxy-D-glucosyl)-L-cysteine (with a purity of >90%, Yield=70%)

(188) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.86 (m, 2H), 7.65 (t, J=7.4 Hz, 1H), 7.59-7.52 (m, 2H), 5.42 (d, J=5.7 Hz, 1H), 5.27 (d, J=10.0 Hz, 1H), 5.14-5.03 (m, 1H), 4.96 (dd, J=10.4, 5.7 Hz, 1H), 4.87-4.72 (m, 2H), 4.38 (m, 1H), 4.34-4.25 (m, 2H), 4.19 (d, J=10.5 Hz, 1H), 3.77 (s, 3H), 3.11 (dd, J=14.0, 6.0 Hz, 1H), 3.04 m, 2H), 2.94 (dd, J=14.0, 6.4 Hz, 1H), 2.10 (s, 3H), 2.05 (s, 3H), 2.05 (s, 3H), 2.03 (s, 3H), 1.44 (s, 9H).

(189) ##STR00129##

(190) Methyl N(N-t-butoxy-L-tryptophanyl)-S-(2,3,4,6-tetraacetoxy-D-glucosyl)-L-cysteine (with a purity of >90%, Yield=81%)

(191) .sup.1H NMR (400 MHz, chloroform-d) 8.81 (s, 1H), 7.63 (d, J=7.9 Hz, 1H), 7.38 (d, J=8.0 Hz, 1H), 7.22-7.15 (m, 1H), 7.15-7.08 (m, 2H), 6.93 (d, J=7.9 Hz, 1H), 5.23-5.14 (t, J=9.8 Hz, 1H), 5.09 (m, 2H), 4.89 (dd, J=10.3, 5.8 Hz, 2H), 4.85-4.79 (m, 1H), 4.58 (s, 1H), 4.24 (dt, J=10.2, 3.7 Hz, 1H), 4.17 (s, 1H), 3.68 (s, 3H), 3.47 (dd, J=14.6, 4.7 Hz, 1H), 3.15 (dd, J=14.6, 6.1 Hz, 1H), 2.95 (dd, J=14.3, 5.6 Hz, 2H), 2.78 (m, 1H), 2.07 (s, 3H), 2.04 (s, 3H), 2.04 (s, 3H), 2.02 (s, 3H), 1.46 (s, 9H).

(192) ##STR00130##

(193) (2,3,4,6-Tetraacetyl-1--D-glucopyranosyl)-L-cysteine methyl ester (with a purity of >90%, Yield=28%).

(194) .sup.1H NMR (400 MHz, chloroform-d) 5.71 (d, J=5.8 Hz, 1H), 5.34 (t, J=9.8 Hz, 1H), 5.07-4.98 (m, 2H), 4.41 (ddd, 1=10.1, 4.8, 2.2 Hz, 1H), 4.29 (dd, J=12.4, 5.1 Hz, 1H), 4.14-4.10 (m, 1H), 3.74 (s, 3H), 3.71 (m, 1H), 2.92 (d, J=5.9 Hz, 2H), 2.10 (s, 3H), 2.07 (s, 3H), 2.04 (s, 3H), 2.01 (s, 3H).

Example 18 Synthesis of S-Glycoside Compound S-18 According to the Present Invention

(195) S-glycosyl compound S18 of the present invention was prepared by the same method as the above route 1, and the route was as follows:

(196) ##STR00131##

(197) Methyl N(N-t-butoxy-L-methioninyl)-S-(2,3,4,6-tetraacetoxy-D-glucosyl)-L-cysteine (with a purity of >90%, Yield=80%)

(198) .sup.1H NMR (400 MHz, chloroform-d) 7.90-7.87 (m, 2H), 7.67-7.62 (m, 1H), 7.55 (m, 2H), 5.68 (d, J=5.8 Hz, 1H), 5.48 (d, J=8.2 Hz, 1H), 5.34-5.28 (m, 1H), 5.08-5.00 (m, 2H), 4.68 (m, 1H), 4.39 (ddd, J=10.0, 4.5, 2.5 Hz, 1H), 4.33 (dd, J=12.3, 4.5 Hz, 1H), 4.16 (dd, J=12.3, 2.5 Hz, 0H), 3.77 (s, 3H), 3.12 (dd, J=14.1, 6.7 Hz, 1H), 2.93 (dd, J=14.0, 5.1 Hz, 1H), 2.52 (t, J=7.4 Hz, 2H), 2.22-2.13 (m, 2H), 2.10 (s, 3H), 2.09 (s, 3H), 2.07 (s, 3H), 2.03 (s, 3H), 2.01 (s, 3H), 1.46 (s, 9H).

(199) Example 19 Synthesis of S-glycoside compounds S-19-S-21 according to the present invention S-glycosyl compounds S-19-S-21 of the present invention were prepared by the same method as the above route 2. The structures and characterization were as follows:

(200) ##STR00132##

(201) Phenyl-2,3,4,6-tetraacetyl-1-S--D-glucopyranose (with a purity of >90%, Yield=84%).

(202) .sup.1H NMR (400 MHz, chloroform-d) 7.46-7.42 (m, 2H), 7.33-7.27 (m, 3H), 5.92 (d, J=5.7 Hz, 0H), 5.48-5.40 (t, J=10.0 Hz, 1H), 5.09 (m, 1H), 4.57 (ddd, J=10.3, 5.2, 2.2 Hz, 1H), 4.28 (dd, J=12.4, 5.2 Hz, 1H), 4.04 (dd, J=12.3, 2.3 Hz, 1H), 2.11 (s, 3H), 2.06 (s, 1H), 2.04 (s, 3H), 2.03 (s, 3H).

(203) ##STR00133##

(204) 2-Pyridinyl-2,3,4,6-tetraacetyl-1-S--D-glucopyranose (with a purity of >90%, Yield=82%).

(205) .sup.1H NMR (400 MHz, chloroform-d) 7.78 (m, 1H), 7.30 (m, 1H), 7.08 (m, 1H), 6.68 (d, J=5.7 Hz, 1H), 5.41 (t, J=9.8 Hz, 1H), 5.26 (dd, J=10.3, 5.7 Hz, 1H), 5.13 (t, J=9.8 Hz, 1H), 4.38 (ddd, J=10.2, 4.5, 2.3 Hz, 1H), 4.27 (dd, J=12.4, 4.6 Hz, 1H), 4.01 (dd, J=12.4, 2.3 Hz, 11H), 2.04 (s, 3H), 2.04 (s, 3H), 2.02 (s, 3H), 1.98 (s, 3H).

(206) ##STR00134##

(207) Methyl-2,3,4,6-tetraacetyl-1-S--D-glucopyranose (with a purity of >90%, Yield=75%).

(208) .sup.1H NMR (400 MHz, chloroform-d) 5.55 (d, J=5.8 Hz, 1H), 5.42-5.36 (t, J=9.8 Hz, 1H), 5.09-5.01 (m, 2H), 4.39 (ddd, J=10.2, 4.9, 2.3 Hz, 1H), 4.30 (dd, J=12.3, 4.9 Hz, 1H), 4.09 (dd, J=12.3, 2.3 Hz, 1H), 2.09 (s, 3H), 2.06 (s, 3H), 2.06 (s, 3H), 2.03 (s, 3H), 2.01 (s, 3H).

(209) Example 20 Synthesis of S-glycoside compound S-23 according to the present invention S-glycosyl compound S23 of the present invention was prepared by the same method as the above route 4. The structures and characterization were as follows:

(210) ##STR00135##

(211) (2,3,4,6-Tetraacetoxy--D-glucosyl)-2,3,4,6-tetraacetoxy-1-S--D-glucoside (with a purity of >90%, Yield=74%).

(212) .sup.1H NMR (400 MHz, chloroform-d) 5.94 (d, J=5.6 Hz, 1H), 5.30 (t, J=9.9 Hz, 1H), 5.20-4.97 (m, 5H), 4.56 (d, J=9.9 Hz, 1H), 4.41-4.38 (m, 2H), 4.20-4.08 (m, 3H), 3.74-3.72 (m, 1H), 2.11, 2.10, 2.03, 2.02, 2.00 (5s, 24H, 8CH.sub.3).

(213) Example 21 Synthesis of S-glycoside compound S-24 according to the present invention S-glycosyl compound S-24 of the present invention was prepared using the following synthetic route. The structure and characterization are as follows:

(214) ##STR00136##

5-Trifluoromethylpyridine-1-S-(2,3,4,6-tetraacetoxy--D-glucosyl)disulfide

(215) .sup.1H NMR (400 MHz, chloroform-d) 8.74-8.51 (s, 1H), 8.02 (d, J=8.5 Hz, 1H), 7.83 (dd, J=8.6, 2.3 Hz, 1H), 5.31-5.20 (m, 2H), 5.10-5.02 (m, 1H), 4.73-4.64 (m, 1H), 4.10-3.95 (m, 2H), 3.70 (ddd, J=10.1, 4.4, 2.8 Hz, 1H), 2.09 (s, 3H), 2.01 (s, 6H), 1.87 (s, 3H).

(216) The specific preparative method was:

(217) At 0 C., 10 mmol I-24 was dissolved in dichloromethane (30 mL), to which were slowly added thioacetic acid (1.7 mL, 24 mmol) and boron trifluoride diethyl etherate (3.7 mL, 30 mmol) dropwise, and then the mixture was warmed to room temperature and stirred overnight. After the raw materials were completely reacted, the reaction was quenched with ice water, extracted with dichloromethane, and washed sequentially with saturated aqueous NaHCO.sub.3 solution and saturated brine. The organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was rotatory evaporated to obtain product II-24.

(218) II-24 and cysteine methyl ester hydrochloride (2.05 g, 12 mmol) were dissolved in DMF (10 mL), to which was added triethylamine (1.7 mL, 12 mmol), and the mixture was stirred at room temperature for 8 h. After II-24 was completely reacted by TLC detection, the mixture was extracted with ethyl acetate, and then washed with half-saturated brine. The organic phase was dried with anhydrous sodium sulfate and filtered. The filtrate was rotatory evaporated and purified by column chromatography to obtain product III-24.

(219) III-24 (1.82 g, 5 mmol) and 2,2-bis(5-trifluoromethylpyridinyl)disulfide (3.6 g, 10 mmol) were dissolved in dichloromethane (20 mL), and the mixture was stirred for 1 h at room temperature. The solvent was rotatory evaporated, and the residue was purified by column chromatography to obtain the product S-24, with a purity of >90% and a three-step yield of 57%.

(220) Synthesis of O-Glycoside Compound

(221) Then, the allylsulfone glycosyl donor prepared above was used as raw material to react with the glycosyl acceptor, to synthesize O-glycosyl compound of the present invention. Specific examples were as follows:

(222) Example 22 Synthesis of O-glycosyl compound O-1 according to the present invention Under nitrogen atmosphere, allylsulfone glycosyl donor (compound 16-1, 1.5 equiv) and glycosyl acceptor (1.0 equiv) were added to the flask for catalytic reaction, to which were added initiator perfluorobutyl iodide (5.0 equiv), diammonium hydrogen phosphate (5.0 equiv), triphenylphosphine oxide (0.3 equiv), and methyl t-butyl ether (0.5 mL), and then the reaction was stirred at room temperature for 24 h under the irradiation of Blue LED, to obtain the O-glycosyl compound 0-1, with a purity of >90%.

(223) ##STR00137##

(224) Characterization of O-glycosyl compound O-1. .sup.1H NMR (400 MHz, chloroform-d) 7.37-7.24 (m, 18H), 7.13 (dd, J=7.3, 2.2 Hz, 2H), 4.96 (d, J=10.8 Hz, 1H), 4.83 (d, J=3.7 Hz, 1H), 4.82-4.77 (m, 2H), 4.74 (d, J=3.6 Hz, 1H), 4.63 (d, J=12.1 Hz, 1H), 4.57 (d, J=12.1 Hz, 1H), 4.48 (d, J=7.5 Hz, 1H), 4.45 (d, J=8.8 Hz, 1H), 3.96 (t, J=9.3 Hz, 1H), 3.84-3.75 (m, 2H), 3.73-3.59 (m, 4H), 3.57 (dd, J=9.7, 3.7 Hz, 1H), 2.61 (t, J=6.5 Hz, 2H); .sup.13C NMR (101 MHz, chloroform-d) 138.78, 138.20, 137.87, 128.59, 128.47, 128.44, 128.23, 128.09, 128.00, 127.96, 127.93, 127.82, 127.78, 127.70, 117.65, 97.78, 81.87, 79.95, 75.83, 75.12, 73.63, 73.57, 70.89, 68.46, 63.22, 18.79.

Example 23 Synthesis of O-Glycosyl Compound O-4 According to the Present Invention

(225) ##STR00138##

(226) Using the same method as that of O-glycosyl compound O-1, the difference was just that the glycosyl acceptor

(227) ##STR00139##
was substituted with

(228) ##STR00140##
to prepare O-glycosyl compound O-4 of the present invention, with a purity of >90%. The structural characterization was as follows:

(229) .sup.1H NMR (400 MHz, chloroform-d) 7.26-7.15 (m, 18H), 7.06 (dd, J=7.4, 2.1 Hz, 2H), 5.21 (d, J=3.7 Hz, 1H), 4.91 (d, J=10.8 Hz, 1H), 4.75 (d, J=10.7 Hz, 1H), 4.72 (d, J=10.9 Hz, 1H), 4.60 (s, 2H), 4.55 (d, J=12.1 Hz, 1H), 4.39 (d, J=8.9 Hz, 1H), 4.36 (d, J=10.3 Hz, 1H), 3.98-3.89 (m, 2H), 3.68 (dd, J=10.5, 3.6 Hz, 1H), 3.60-3.50 (m, 2H), 3.46 (dd, J=9.7, 3.7 Hz, 1H), 2.05 (t, J=3.2 Hz, 3H), 1.76 (dt, J=13.9, 11.2 Hz, 6H), 1.53 (q, J=5.5, 4.7 Hz, 6H); .sup.13C NMR (101 MHz, chloroform-d) 139.14, 138.44, 138.39, 138.17, 128.40, 128.37, 128.33, 128.17, 128.00, 127.92, 127.86, 127.77, 127.69, 127.61, 127.49, 89.90, 82.14, 80.17, 78.23, 75.56, 75.12, 74.58, 73.49, 72.89, 69.76, 68.88, 42.52, 36.35, 30.72.

Example 24 Synthesis of O-Glycosyl Compound O-10 According to the Present Invention

(230) ##STR00141##

(231) Using the same method as that of O-glycosyl compound O-1, the difference was just that the glycosyl acceptor

(232) ##STR00142##
was substituted with

(233) ##STR00143##
to prepare O-glycosyl compound 0-10 of the present invention, with a purity of >90%. The structural characterization was as follows: .sup.1H NMR (400 MHz, chloroform-d) 7.62 (d, J=1.7 Hz, 1H), 7.55 (d, J=8.5 Hz, 1H), 7.45 (d, J=8.8 Hz, 1H), 7.34 (dd, J=8.5, 1.9 Hz, 1H), 7.32-7.22 (m, 13H), 7.20 (d, J=6.4 Hz, 2H), 7.13 (ddd, J=11.5, 6.9, 2.0 Hz, 4H), 7.07 (dd, J=6.7, 2.9 Hz, 2H), 7.06-7.00 (m, 2H), 6.43 (d, J=3.2 Hz, 1H), 4.73 (d, J=10.8 Hz, 1H), 4.57 (t, J=11.9 Hz, 2H), 4.48-4.38 (m, 4H), 4.31 (d, J=11.1 Hz, 1H), 3.91 (q, I=7.1 Hz, 1H), 3.83 (s, 3H), 3.79 (ddd, J=9.9, 3.6, 2.1 Hz, 1H), 3.68-3.61 (m, 1H), 3.60 (d, J=2.2 Hz, 1H), 3.59-3.53 (m, 2H), 3.48 (t, J=9.2 Hz, 1H), 1.59 (d, J=7.1 Hz, 3H); .sup.13C NMR (100 MHz, chloroform-d) 172.81, 157.58, 138.63, 138.12, 137.86, 137.72, 135.36, 133.69, 129.35, 128.90, 128.41, 128.38, 128.28, 128.27, 128.16, 127.95, 127.80, 127.75, 127.49, 126.96, 126.74, 126.26, 118.82, 105.54, 90.45, 81.22, 79.47, 76.70, 75.36, 75.07, 73.52, 73.19, 72.98, 68.22, 55.26, 55.24, 45.51, 18.03.
Synthesis of C-Glycosyl Compound:

(234) Then, the allylsulfone glycosyl donor prepared above was used as raw material to react with the glycosyl acceptor, to synthesize C-glycosyl compound of the present invention. For example, using the above compound 3-1 as a raw material, the synthetic route was as follows:

(235) ##STR00144##

(236) Under nitrogen atmosphere, glycosyl donor 3-1 (1.0 equiv), glycosyl acceptor pyridium tetrafluoroborate (2.0 equiv), photosensitizer EosinY (0.025 equiv), and initiator sodium trifluoromethylsulfinate (0.2 equiv.) were added to the flask for catalytic reaction, to which was added DMSO, and the reaction was stirred at room temperature for 8 h under the irradiation of Blue LED, to obtain the C-glycosyl compound CX.

(237) The following was specific examples of synthesizing C-glycosyl compounds:

Example 25 Synthesis of C-Glycosyl Compound According to the Present Invention

(238) Using the same method as the above route, C-glycosyl compounds C-1, C-2, C-4, C-6, C-8 of the present invention were prepared, and the structure and characterization were as follows:

(239) ##STR00145##

(240) (2R,3R,4R,5S,6R)-2-(acetoxymethyl)-6-(4-cyanopyridin-2-yl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (C-1), with a purity of >90%. .sup.1H NMR (400 MHz, chloroform-d) 8.84 (d, J=5.0 Hz, 1H), 7.68 (d, J=1.5 Hz, 1H), 7.53 (d, J=5.0 Hz, 1H), 5.78 (t, J=6.6 Hz, 1H), 5.50-5.26 (m, 2H), 5.21-5.00 (m, 1H), 4.58-4.32 (m, 2H), 4.23-4.05 (m, 1H), 2.18-2.00 (m, 9H), 1.85 (d, J=1.2 Hz, 3H).

(241) ##STR00146##

(242) (2R,3S,4R,5S,6R)-2-(acetoxymethyl)-6-(4-cyanopyridin-2-yl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (C-2), with a purity of >90%. .sup.1H NMR (400 MHz, chloroform-d) 8.74 (d, J=5.0 Hz, 1H), 7.61 (s, 1H), 7.45 (dd, J=4.9, 1.5 Hz, 1H), 5.69 (dd, J=6.8, 3.3 Hz, 1H), 5.57-5.42 (m, 2H), 5.34 (d, J=4.1 Hz, 1H), 4.64-4.56 (m, 1H), 4.50 (dd, J=12.0, 8.4 Hz, 1H), 4.11 (dd, J=12.0, 4.2 Hz, 1H), 2.09 (d, J=4.5 Hz, 6H), 2.00 (s, 3H), 1.81 (s, 3H).

(243) ##STR00147##

(244) (2R,3R,4S,5R,6R)-2-(acetoxymethyl)-6-(((2R,3R,4S,5S,6R)-4,5-diacetoxy-2-(acetoxymethyl)-6-(4-cyanopyridin-2-yl)tetrahydro-2H-pyran-3-yl)oxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate (C4), with a purity of >90%. .sup.1H NMR (400 MHz, chloroform-d) 8.83-8.69 (m, 1H), 7.79 (s, 1H), 7.48 (dd, J=5.0, 1.5 Hz, 1H), 5.81-5.61 (m, 1H), 5.44-5.34 (m, 2H), 5.28 (d, J=3.9 Hz, 1H), 5.17 (dd, J=10.4, 7.8 Hz, 1H), 5.03 (dd, J=10.5, 3.4 Hz, 1H), 4.69 (d, J=7.9 Hz, 1H), 4.32 (s, 3H), 4.11 (dd, J=6.7, 3.0 Hz, 2H), 3.99 (t, J=6.7 Hz, 1H), 3.82-3.67 (m, 1H), 2.18-2.11 (m, 9H), 2.09 (s, 3H), 2.05 (s, 3H), 1.98 (s, 3H), 1.85 (s, 3H).

(245) ##STR00148##

(246) (2R,3R,4R,5S,6R)-2-(acetoxymethyl)-6-(4-(trifluoromethyl)pyridin-2-yl)tetrahydro-2H-pyran-3,4,5-triyl triacetate(C-6), with a purity of >90%. .sup.1H NMR (400 MHz, chloroform-d) 8.85 (d, J=5.1 Hz, 1H), 7.63 (s, 1H), 7.51 (dd, J=5.1, 1.6 Hz, 1H), 5.86 (t, J=6.4 Hz, 1H), 5.38 (d, J=6.4 Hz, 2H), 5.11 (t, J=7.2 Hz, 1H), 4.48 (ddd, J=7.9, 5.8, 3.1 Hz, 1H), 4.38 (dd, J=12.2, 5.8 Hz, 1H), 4.12 (dd, J=12.2, 3.2 Hz, 1H), 2.19-2.00 (m, 9H), 1.83 (s, 3H).

(247) ##STR00149##

(248) (2R,3R,4R,5S,6R)-2-(acetoxymethyl)-6-(pyridin-2-yl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (C-8). .sup.1H NMR (400 MHz, chloroform-d) 8.68 (dd, J=4.8, 1.7 Hz, 1H), 7.71 (td, J=7.7, 1.8 Hz, 1H), 7.33 (d, J=7.8 Hz, 1H), 7.28 (q, J=5.0, 4.3 Hz, 1H), 6.17 (t, J=8.1 Hz, 1H), 5.39-5.24 (m, 2H), 5.16 (t, J=8.4 Hz, 1H), 4.62-4.48 (m, 1H), 4.30 (dd, J=12.3, 4.7 Hz, 1H), 4.06 (dd, J=12.3, 2.8 Hz, 1H), 2.07 (d, J=3.7 Hz, 9H), 1.82 (s, 3H).

(249) In summary, the present invention provided a glycosyl donor represented by formula I and a preparative method thereof, as well as the use of the glycosyl donor of formula I in the preparation of S-glycoside represented by formula III, O-glycoside represented by formula IV, and C-glycoside represented by formula V. The glycosyl donor provided by the present invention had a novel structure, that could be prepared by a simple method. In the present invention, the above-mentioned glycosyl donor was further used as a starting material, and by a free radical reaction, O-glycoside, S-glycoside, and C-glycoside compounds were prepared, most of which had a special configuration. The preparative method was simple, the reaction conditions were mild, and the reaction had a high yield, that all indicated promising application prospects.