Sulfinate glycosyl donor, method for preparing same, and use thereof

Abstract

A sulfinate glycosyl donor of formula I and a method for preparing same as well as use thereof in preparing a glycoside compound including a thioglycoside compound and a carbon glycoside compound are provided. The sulfinate glycosyl donor has a special sulfinate structure. When the sulfinate glycosyl donor is used as a raw material to prepare the glycoside compound, an additional initiator does not need to be added, such that the production cost is saved, the generation of byproducts is reduced, and the glycoside compound with a purity greater than 98% is obtained. The sulfinate glycosyl donor can be used in the preparation of the glycoside compound such as the thioglycoside compound and the carbon glycoside compound.

Claims

1. A glycosyl donor, or salts thereof, or stereoisomers thereof, or optical isomers thereof, characterized in that the structure of the glycosyl donor is as represented by formula W: ##STR00097## wherein, n is selected from 0 or 1; a is selected from 3 or 4; R is each independently selected from L.sub.1R.sub.x; or two adjacent R are linked to form a ring, while the other R is each independently selected from L.sub.1R.sub.x. The ring is either unsubstituted or substituted with one or more L.sub.1R.sub.x; L.sub.1 is selected from absence or C.sub.1-2 alkylene, and R.sub.x is selected from the group consisting of H, OH, C.sub.1-6 alkyl, OAc, OBn, OR.sub.8, NR.sub.9R.sub.10, ##STR00098## Ph, amino, ##STR00099## and ##STR00100## i is an integer selected from 0 to 6; R.sub.11, R.sub.12, R.sub.13, and R.sub.14 are each independently selected from L.sub.2R.sub.y; L.sub.2 is selected from absence or C.sub.1-2 alkylene, and R.sub.y is selected from the group consisting of H, OH, C.sub.1-6 alkyl, OAc, OBn, OR.sub.8, and NR.sub.9R.sub.10; R.sub.8 is selected from C.sub.1-6 alkyl; R.sub.9 is selected from the group consisting of H, C.sub.1-6 alkyl, Ac, and Bn; R.sub.10 is selected from the group consisting of H, C.sub.1-6 alkyl, Ac, and Bn; j is selected from 1, 2, or 3; M.sup.j+ is a j-valent cation.

2. The glycosyl donor according to claim 1, or salts thereof, or stereoisomers thereof, or optical isomers thereof, characterized in that the structure of the glycosyl donor is as represented by formula I: ##STR00101## wherein, n is selected from 0 or 1; a is selected from 3 or 4; R is each independently selected from L.sub.1R.sub.x; or two adjacent R are linked to form a ring, while the other R is each independently selected from L.sub.1R.sub.x. The ring is either unsubstituted or substituted with one or more L.sub.1R.sub.x; L.sub.1 is selected from absence or C.sub.1-2 alkylene, and R.sub.x is selected from the group consisting of H, OH, C.sub.1-6 alkyl, OAc, OBn, OR.sub.8, NR.sub.9R.sub.10, ##STR00102## Ph, amino, ##STR00103## and ##STR00104## i is an integer selected from 0 to 6; R.sub.11, R.sub.12, R.sub.13, and R.sub.14 are each independently selected from L.sub.2R.sub.y; L.sub.2 is selected from absence or C.sub.1-2 alkylene, and R.sub.y is selected from the group consisting of H, OH, C.sub.1-6 alkyl, OAc, OBn, OR.sub.8, and NR.sub.9R.sub.10; R.sub.8 is selected from C.sub.1-6 alkyl; R.sub.9 is selected from the group consisting of H, C.sub.1-6 alkyl, Ac, and Bn; R.sub.10 is selected from the group consisting of H, C.sub.1-6 alkyl, Ac, and Bn; M.sup.+ is a monovalent cation.

3. The glycosyl donor according to claim 2, or salts thereof, or stereoisomers thereof, or optical isomers thereof, characterized in that the structure of the glycosyl donor is as represented by formula II: ##STR00105## wherein, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently selected from L.sub.1R.sub.x; alternatively, for R.sub.1, R.sub.2, R.sub.3, and R.sub.4, two adjacent groups are linked to form a ring, and the remaining two groups are each independently selected from L.sub.1R.sub.x. The ring is a 5-6-membered ring which is unsubstituted or substituted with one or more L.sub.1R.sub.x; L.sub.1 is selected from absence or methylene, and R.sub.x is selected from the group consisting of H, OH, C.sub.1-5 alkyl, OAc, OBn, OR.sub.8, NR.sub.9R.sub.10, ##STR00106## Ph, amino, ##STR00107## and ##STR00108## i is an integer selected from 0 to 4; R.sub.11, R.sub.12, R.sub.13, and R.sub.14 are each independently selected from L.sub.2R.sub.y; L.sub.2 is selected from absence or methylene, and R.sub.y is selected from the group consisting of H, OH, C.sub.1-5 alkyl, OAc, OBn, OR.sub.8, and NR.sub.9R.sub.10; R.sub.8 is selected from C.sub.1-5 alkyl; R.sub.9 is selected from the group consisting of H, C.sub.1-5 alkyl, Ac, and Bn; R.sub.10 is selected from the group consisting of H, C.sub.1-5 alkyl, Ac, and Bn; M.sup.+ is a monovalent cation.

4. The glycosyl donor according to claim 2, or salts thereof, or stereoisomers thereof, or optical isomers thereof, characterized in that the structure of the glycosyl donor is as represented by formula III: ##STR00109## wherein, R.sub.5, R.sub.6, and R.sub.7 are each independently selected from L.sub.1R.sub.x; alternatively, for R.sub.5, R.sub.6, and R.sub.7, two adjacent groups are linked to form a ring, and the remaining group is L.sub.1R.sub.x. The ring is a 5-6-membered ring that is unsubstituted or substituted with one or more L.sub.1R.sub.x; L.sub.1 is selected from absence or methylene, and R.sub.x is selected from the group consisting of H, OH, C.sub.1-5 alkyl, OAc, OBn, OR.sub.8, NR.sub.9R.sub.10, ##STR00110## Ph, amino, ##STR00111## and ##STR00112## i is an integer selected from 0 to 4; R.sub.11, R.sub.12, R.sub.13, and R.sub.14 are each independently selected from L.sub.2R.sub.y; L.sub.2 is selected from absence or methylene, and R.sub.y is selected from the group consisting of H, OH, C.sub.1-5 alkyl, OAc, OBn, OR.sub.8, and NR.sub.9R.sub.10; R.sub.8 is selected from C.sub.1-5 alkyl; R.sub.9 is selected from the group consisting of H, C.sub.1-5 alkyl, Ac, and Bn; R.sub.10 is selected from the group consisting of H, C.sub.1-5 alkyl, Ac, and Bn; M.sup.+ is a monovalent cation.

5. The glycosyl donor according to claim 3, or salts thereof, or stereoisomers thereof, or optical isomers thereof, characterized in that the 5-6-membered ring is a 5-6-membered saturated oxygen-containing heterocycle; R.sub.8 is selected from C.sub.1-3 alkyl; R.sub.9 is selected from the group consisting of H, C.sub.1-3 alkyl, Ac, and Bn; R.sub.10 is selected from the group consisting of H, C.sub.1-3 alkyl, Ac, and Bn; M.sup.+ is selected from the group consisting of Na.sup.+, K.sup.+, and Li.sup.+.

6. The glycosyl donor according to claim 1, or salts thereof, or stereoisomers thereof, or optical isomers thereof, characterized in that the structure of the glycosyl donor is selected from the group consisting of: ##STR00113## ##STR00114## ##STR00115##

7. A method for preparing the glycosyl donor according to claim 1, characterized in that the method comprises the following steps: ##STR00116## (1) The compound represented by formula A reacts with the compound represented by formula B, to obtain the compound represented by formula C; (2) The compound represented by formula C reacts with m-chloroperoxybenzoic acid, to obtain the compound represented by formula D; (3) The compound represented by formula D reacts with (MeO.sup.).sub.jM.sup.j+, to obtain the compound represented by formula W; wherein n, a, R, M.sup.j+, and j are as defined in claim 1.

8. The method according to claim 7, characterized in that in step (1), the molar ratio of the compound represented by formula A to the compound represented by formula B is 1:(1.0-2.0), the reaction is carried out in the presence of Lewis acid, the molar ratio of the compound represented by formula A to Lewis acid is 1:(1.0-3.0), the reaction solvent is an organic solvent, the reaction temperature is room temperature, and the reaction time is 0.5-3 h; in step (2), the molar ratio of the compound represented by formula A to m-chloroperoxybenzoic acid is 1:(2-4), the reaction solvent is an organic solvent, the reaction temperature is room temperature, and the reaction time is 0.5-3 h; in step (3), the molar ratio of the compound represented by formula A to (MeO.sup.).sub.jM.sup.j+ is 1:(0.5-1.5), the reaction solvent is an organic solvent, the reaction temperature is 5 C. to 5 C., and the reaction time is 1-3 h.

9. The method according to claim 8, characterized in that in step (1), the molar ratio of the compound represented by formula A to the compound represented by formula B is 1:1.2, Lewis acid is BF.sub.3.Math.Et.sub.2O, the molar ratio of the compound represented by formula A to Lewis acid is 1:2.0, the organic solvent is dichloromethane, and the reaction time is 1 h; in step (2), the molar ratio of the compound represented by formula A to m-chloroperoxybenzoic acid is 1:3, the organic solvent is dichloromethane, and the reaction time is 1 h; in step (3), the molar ratio of the compound represented by formula A to (MeO.sup.).sub.jM.sup.j+ is 1:1, the organic solvent is methanol, the reaction temperature is 0 C., and the reaction time is 2 h.

10. The use of the glycosyl donor according to claim 1 in the preparation of glycoside compounds; the glycoside compound is preferably a S-glycoside compound or a C-glycoside compound.

11. The use according to claim 10, characterized in that the C-glycoside compound comprises aryl C-glycoside compounds.

12. A method for preparing a C-glycoside compound, characterized in that the method comprises the following steps: the glycosyl donor according to claim 1, the glycosyl acceptor represented by formula A-1, and a photosensitizer are added to a solvent, and then allowed to react under light, to obtain the C-glycoside compound represented by formula A-2; ##STR00117## wherein R, a, and n are as defined in claim 1; R.sub.a1 is selected from the group consisting of H, hydroxyl, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, halogen, and the following moieties unsubstituted or substituted with one or more R.sub.a2 groups: 5-6-membered aryl, 5-6-membered heteroaryl, 3-8-membered saturated cycloalkyl, 3-8-membered saturated heterocyclyl; R.sub.a2 is selected from the group consisting of hydroxyl, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, halogen, COOR.sub.a3, COR.sub.a3; R.sub.a3 is selected from H and C.sub.1-6 alkyl.

13. The method according to claim 12, characterized in that the molar ratio of the glycosyl donor, the glycosyl acceptor represented by formula A-1, and a photosensitizer is 1:(1-3):(5-20), and preferably 1:1.5:10; the photosensitizer is selected from the group consisting of Ru (II) photosensitizer, eosin Y or a salt thereof, and said Ru (II) photosensitizer is preferably Ru(bpy).sub.3Cl.sub.2.Math.6H.sub.2O, and the salt of eosin Y is preferably Eosin Y/Na.sup.+; the solvent is an organic solvent; and preferably DMSO, DMF, DMA; and more preferably DMSO; the reaction is carried out under a nitrogen atmosphere, the reaction temperature is room temperature, and the reaction time is 10-14 h; said R.sub.a1 is ##STR00118##

14. A method for preparing a S-glycoside compound, characterized in that the method comprises the following steps: the glycosyl donor according to claim 1, the glycosyl acceptor represented by formula C-1, and a photosensitizer are added to a solvent, and then allowed to react under light, to obtain the S-glycoside compound represented by formula C-2; ##STR00119## wherein R, a, and n are as defined in claim 1; R.sub.c1 is selected from the group consisting of H, hydroxyl, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, halogen, and the following moieties unsubstituted or substituted with one or more R.sub.c2 groups: 5-6-membered aryl, 5-6-membered heteroaryl, 3-8-membered saturated cycloalkyl, 3-8-membered saturated heterocyclyl; R.sub.c2 is selected from the group consisting of hydroxyl, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, halogen, COOR.sub.c3, COR.sub.c3; R.sub.c3 is selected from H and C.sub.1-6 alkyl.

15. The method according to claim 14, characterized in that the molar ratio of the glycosyl donor, the glycosyl acceptor represented by formula C-1, and a photosensitizer is 1:(1-3):(5-20), and preferably 1:1.5:10; the photosensitizer is selected from the group consisting of Ru (II) photosensitizer, eosin Y or a salt thereof, and said Ru (II) photosensitizer is preferably Ru(bpy).sub.3Cl.sub.2.Math.6H.sub.2O, and the salt of eosin Y is preferably Eosin Y/Na.sup.+; the solvent is an organic solvent; and preferably DMSO, DMF, DMA; and more preferably DMSO; the reaction is carried out under a nitrogen atmosphere, the reaction temperature is room temperature, and the reaction time is 10-14 h; said R.sub.c1 is ##STR00120##

Description

EXAMPLES

[0090] The starting materials and equipment used in the specific examples of the present invention are all known products, which are obtained by purchasing those commercially available.

[0091] The sodium sulfinate glycosyl donor of the present invention was prepared using the following synthetic route:

##STR00027## ##STR00028## ##STR00029##

Example 1: Preparation of Sodium Sulfinate Glycosyl Donors 1-20

I. Preparation of Sodium Sulfinate Glycosyl Donor 1

##STR00030##

Specific procedures were as follows:

[0092] Step 1: To a 100 mL round bottom flask containing SI-1 (3.9 g, 10 mmol, 1.0 equiv) and 25 mL of CH.sub.2Cl.sub.2, were added methyl 3-mercaptopropionate (1.3 mL, 12 mmol, 1.2 equiv) and BF.sub.3.Math.Et.sub.2O (2.5 mL, 20 mmol, 2.0 equiv) sequentially. The reaction solution was stirred at room temperature for 1 h, until SI-1 was completely disappeared by TLC detection, and then washed with saturated NaHCO.sub.3 aqueous solution to be neutral. The organic layers were separated, washed with saline, dried over anhydrous Na.sub.2SO.sub.4, and then concentrated to obtain SI-2, which could be directly used for the next step without purification.

[0093] Step 2: SI-2 was dissolved in 20 mL of CH.sub.2Cl.sub.2 and then cooled at 0 C. m-CPBA (m-chloroperoxybenzoic acid, 6 g, 30 mmol, 3 equiv) was slowly added to the reaction solution under stirring. The mixed solution was stirred at room temperature for 1 h and filtered. The filtrate was washed with saturated NaHCO.sub.3 solution until neutral, dried over anhydrous Na.sub.2SO.sub.4, and concentrated. Methyl tert-butyl ether was added to precipitate the solid, which was collected by filtration to obtain SI-3 as white solid.

[0094] Step 3: SI-3 was dissolved in 20 mL of MeOH at 0 C., to which was added MeONa (540 mg, 10 mmol, 1.0 equiv), and then the reaction was stirred at 0 C. for 2 h. TLC detection indicated that SI-3 was completely consumed before concentration. The residue was washed with absolute ethanol, and then the resultant solution was filtered to obtain white solid, namely sodium sulfinate glycosyl donor 1. The total yield for three steps was 85%.

II. Preparation of Sodium Sulfinate Glycosyl Donors 2-20

[0095] Sodium sulfinate glycosyl donors 2-20 were prepared separately by referring to the above method for preparing sodium sulfinate glycosyl donor 1, with the only difference lying in that the raw material SI-1 was substituted with the corresponding starting materials, respectively.

[0096] The structure and characterization of sodium sulfinate glycosyl donors 1-20 are shown in Table 1. The total yield for three steps and the purity of sodium sulfinate glycosyl donors 1-20 are shown in Table 2.

TABLE-US-00001 TABLE 1 The structure and characterization of sodium sulfinate glycosyl donors 1-20. Starting materials No Structure corresponding to SI-1 Structural characterization 1 [00031] [00032] .sup.1H NMR (400 MHz, CD.sub.3OD) 3.85 (d, J = 12.9 Hz, 1H), 3.73 (t, J = 9.3 Hz, 1H), 3.66 (dd, J = 12.0, 5.2 Hz, 1H), 3.43 (t, J = 8.4 Hz, 1H), 3.35 (d, J = 9.7 Hz, 1H), 3.30 (d, J = 5.3 Hz, 2H); .sup.13C NMR (101 MHz, D.sub.2O) 92.68, 79.99, 77.10, 69.76, 69.16, 60.94. 2 [00033] [00034] .sup.13C NMR (101 MHz, D.sub.2O) 96.29, 76.96, 70.67, 68.55, 60.78, 31.38. 3 [00035] [00036] .sup.1H NMR (400 MHz, CD.sub.3OD) 3.99 (t, J = 9.5 Hz, 1H), 3.83 (dd, J = 11.7, 7.7 Hz, 1H), 3.78 (d, J = 3.3 Hz, 1H), 3.66 3.60 (m, 1H), 3.58 (q, J = 3.9 Hz, 1H), 3.53 (dd, J = 9.4, 3.4 Hz, 1H), 3.34 (d, J = 3.5 Hz, 1H). .sup.13C NMR (101 MHz, D.sub.2O) 93.72, 79.49, 73.96, 69.08, 67.06, 61.60. 4 [00037] [00038] .sup.1H NMR (400 MHz, D.sub.2O) 4.22 (d, J = 3.0 Hz, 1H), 3.78 (m, 2H), 3.71 3.62 (m, 3H), 3.50 (d, J = 1.3 Hz, 1H); .sup.13C NMR (101 MHz, D.sub.2O) 100.65, 77.55, 71.25, 67.94, 66.20, 61.06 5 [00039] [00040] .sup.1H NMR (400 MHz, D.sub.2O) 4.33 4.29 (m, 1H), 4.20 4.10 (m, 1H), 3.85 3.76 (m, 2H), 3.52 3.45 (m, 1H), 1.31 (d, J = 6.1, 3H). .sup.13C NMR (101 MHz, D.sub.2O) 90.32, 71.66, 69.90, 68.21, 57.41, 16.76. 6 [00041] [00042] .sup.1H NMR (400 MHz, D.sub.2O) 3.86 3.80 (m, 1H), 3.72 (d, J = 6.3 Hz, 1H), 3.62 (dt, J = 10.6, 2.9 Hz, 1H), 3.56 (td, J = 7.1, 1.9 Hz, 1H), 3.39 (dd, J = 9.7, 1.9 Hz, 1H), 1.22 1.17 (m, 3H); .sup.13C NMR (101 MHz, D.sub.2O) 93.75, 75.19, 74.10, 71.61, 66.57, 16.78. 7 [00043] [00044] .sup.13C NMR (101 MHz, D.sub.2O) 99.50, 73.85, 70.79, 69.85, 68.38. 8 [00045] [00046] Mixture of a and b.sup.1H NMR (400 MHz, D.sub.2O) 4.37 (td, J = 3.9, 1.3 Hz, 0.5 H), 4.03 3.83 (m, 3H), 3.75 3.54 (m, 2.5H); .sup.13C NMR (101 MHz, D.sub.2O) 96.71, 72.41, 71.81, 70.31, 68.44. 9 [00047] [00048] .sup.1H NMR (400 MHz, D.sub.2O) 3.98 (dd, J = 11.1, 5.3 Hz, 1H), 3.60 (t, J = 9.2 Hz, 1H), 3.52 (td, J = 9.7, 5.2 Hz, 1H), 3.42 (t, J = 9.2 Hz, 2H), 3.22 (t, J = 10.8 Hz, 1H); .sup.13C NMR (101 MHz, D.sub.2O) 93.61, 77.12, 69.54, 69.15, 68.86. 10 [00049] [00050] Mixture of : = 5:4, .sup.1H NMR (400 MHz, D.sub.2O): 4.43 (t, J = 4.2 Hz, 0.43H), 4.29 (dd, J = 4.7, 2.1 Hz, 1H), 4.05 (dd, J = 8.4, 4.5 Hz, 0.55H), 4.00-3.91 (m, 2.46H), 3.88-3.68 (m, 2.94H), and 3.58 (td, J = 12.4, 4.7 Hz, 1.74H); .sup.13C NMR (101 MHz, D.sub.2O): 102.18, 100.63, 83.01, 82.53, 71.53, 71.30, 71.16, 70.70, 61.70, and 60.76., 2.89 (t, J = 6.9 Hz, 0.5H)..sup.13C NMR (101 MHz, D.sub.2O) 102.09, 83.05, 71.29, 70.67, 61.67. 11 [00051] [00052] .sup.1H NMR (400 MHz, Methanol-d.sub.4) 4.28 (d, J = 5.0 Hz, 1H), 3.96 (t, J = 6.3 Hz, 1H), 3.81 (t, J = 1.8 Hz, 1H), 3.73 3.65 (m, 1H), 1.21 (d, J = 6.3 Hz, 3H); .sup.13C NMR (101 MHz, D.sub.2O) 101.85, 78.88, 76.35, 70.51, 17.67. 12 [00053] [00054] .sup.1H NMR (400 MHz, CD.sub.3OD) 5.01 (t, J = 4.5 Hz, 1H), 4.45 (d, J = 6.4 Hz, 1H), 4.20 (q, J = 7.1 Hz, 1H), 3.62 (dd, J = 4.4, 1.7 Hz, 1H), 1.46 (s, 3H), 1.30 (s, 3H), 1.15 (d, J = 5.1 Hz, 3H). 13 [00055] [00056] .sup.1H NMR (400 MHz, D.sub.2O) 5.32 (d, J = 3.8 Hz, 1H), 3.86 (d, J = 11.7 Hz, 1H), 3.81 3.44 (m, 11H), 3.33 (t, J = 9.4 Hz, 1H); .sup.13C NMR (101 MHz, D.sub.2O) 99.67, 92.47, 78.56, 77.51, 76.44, 72.83, 72.66, 71.73, 69.62, 69.30, 60.94, 60.43. 14 [00057] [00058] only .sup.1H NMR (400 MHz, CDCl3 with 1%.sub.o TFA): 7.36 7.27 (m, 14H), 7.26 7.22 (m, 4H), 7.15 7.06 (m, 2H), 4.93 (d, J = 11.1 Hz, 1H), 4.89 (d, J = 11.1 Hz, 1H), 4.81 (d, J = 10.7 Hz, 1H), 4.76 (d, J =11.1 Hz, 1H), 4.68 (d, J = 10.6 Hz, 1H), 4.44 (d, J = 11.3 Hz, 1H), 4.41 (d, J = 11.1 Hz, 1H), 4.36 (d,J = 11.2 Hz, 1H), 4.11 (d, J = 9.7 Hz, 1H), 3.85 (t, J = 8.8 Hz, 1H), 3.77 (t, J = 9.4 Hz, 1H), 3.67 (ddt, J = 7.9, 4.8, 2.9 Hz, 2H), 3.60 3.54 (m, 1H), and 3.51 (dd, J = 10.7, 5.4 Hz, 1H); .sup.13C NMR (101 MHz, CDCl3 with 1%.sub.o TFA): 161.1, 160.7, 160.2, 159.8, 137.0, 136.5, 136.3, 135.3, 129.0, 128.9, 128.7, 128.7, 128.6, 128.6, 128.5, 128.4, 128.3, 128.0, 118.7, 115. 9, 113.1, 110.2, 92.0, 85.7, 78.4, 77.3, 77.0, 76.8, 76.7, 76.1, 75.6, 75.4, 73.8, and 67.9. 15 [00059] [00060] .sup.1H NMR (400 MHz, D.sub.2O) 3.92 (d, J = 13.0 Hz, 1H), 3.76 (dd, J = 12.5, 4.9 Hz, 1H), 3.71 (d, J = 10.3 Hz, 1H), 3.68 3.60 (m, 1H), 3.48 (ddd, J = 22.8, 17.9, 9.0 Hz, 2H), 3.39 3.31 (m, 1H). 16 [00061] [00062] .sup.1H NMR (400 MHz, MeOD) 7.84 (s, 2H), 7.77 (dd, J = 5.5, 3.1 Hz, 2H), 4.29 (dd, J = 6.7, 2.8 Hz, 2H), 4.13 (dd, J = 7.2, 3.3 Hz, 1H), 3.93 (dd, J = 12.1, 2.1 Hz, 1H), 3.73 3.67 (m, 1H), 3.46 (ddd, J = 9.3, 6.7, 2.2 Hz, 1H), 3.34 (s, 1H). 17 [00063] [00064] .sup.1H NMR (400 MHz, MeOD) 7.48 (dd, J = 6.8, 3.1 Hz, 2H), 7.41 (d, J = 2.5 Hz, 2H), 7.40 7.39 (m, 1H), 5.68 (s, 1H), 4.31 (td, 1H), 3.82 (t, J = 10.2 Hz, 1H), 3.78 3.72 (m, 2H), 3.60 (dqd, J = 9.3, 7.8, 7.3, 3.6 Hz, 3H). 18 [00065] [00066] .sup.1H NMR (400 CD.sub.3OD) 3.85 (d, J = 12.9 Hz, 1H), 3.73 (t, J = 9.3 Hz, 1H), 3.66 (dd, J = 12.0, 5.2 Hz, 1H), 3.43 (t, J = 8.4 Hz, 1H), 3.35 (d, J = 9.7 Hz, 1H), 3.30 (d, J = 5.3 Hz, 2H) 19 [00067] [00068] .sup.1H NMR (400 MHz, CD.sub.3OD) 7.83 7.76 (m, 1H), 7.55 7.50 (m, 1H), 7.47 (d, J = 4.5 Hz, 2H), 4.16 (t, J = 10.3 Hz, 1H), 3.90 (d, J = 12.1 Hz, 1H), 3.79 3.75 (m, 1H), 3.74 3.67 (m, 11H), 3.36 3.32 (m, 1H). 20 [00069] [00070] .sup.1H NMR (400 MHz, D.sub.2O) 3.94 (t, J = 10.3 Hz, 2H), 3.86 3.76 (m, 3H), 3.76 3.67 (m, 14H), 3.61 (d, J = 10.6 Hz, 2H), 3.54 3.50 (m, 2H), 3.49 3.42 (m, 2H), 2.58 (t, J = 6.2 Hz, 2H).

TABLE-US-00002 TABLE 2 The total yield for three steps and the purity of sodium sulfinate glycosyl donors 1-20. Total yield for No. Structure three steps Purity 1 [00071] 85% 99% 2 [00072] 77% 95% 3 [00073] 87% 98% 4 [00074] 75% 98% 5 [00075] 67% 90% 6 [00076] 70% 90% 7 [00077] 70% 90% 8 [00078] 70% 90% 9 [00079] 70% 90% 10 [00080] 65% 85% 11 [00081] 85% 95% 12 [00082] 60% 90% 13 [00083] 75% 95% 14 [00084] 85% 98% 15 [00085] 82% 98% 16 [00086] 85% 98% 17 [00087] 70% 97% 18 [00088] 85% 98% 19 [00089] 70% 85% 20 [00090] 57% 98%

Example 2: Preparation of Non-Aryl C-Glycosides Using Sodium Sulfinate Glycosyl Donors as Raw Materials

##STR00091##

[0097] C-glycosides were synthesized according to the above route, and the specific procedures were as follows: Glycosyl donor 1 (0.2 mmol), 4-methoxycarbonylstyrene (0.3 mmol), photosensitizer Ru(bpy).sub.3Cl.sub.2.Math.6H.sub.2O (1 mol %), and DMSO (0.5 mL) were weighed, transferred into a vial with a spiral cap and a magnetic stirring bar, and then mixed. The vial was filled with N.sub.2 and sealed with a Teflon cap. The mixture was stirred at room temperature under a 10 W, 455 nm LED light for 12 h to complete the reaction.

[0098] The reaction solution was freeze-dried and subjected to column chromatography, to obtain C-glycoside compounds as pure -configuration, with a yield of 90% and a purity of >98%. The structural characterization was as follows:

##STR00092##

[0099] .sup.1H NMR (400 MHZ, DMSO-d.sub.6) 7.88 (d, J=7.9 Hz, 2H), 7.38 (d, J=7.9 Hz, 2H), 4.89 (d, J=4.4 Hz, 1H), 4.81 (d, J=5.3 Hz, 2H), 4.48 (t, J=6.0 Hz, 1H), 3.84 (s, 3H), 3.73-3.61 (m, 2H), 3.46-3.41 (m, 1H), 3.32-3.28 (m, 1H), 3.02 (td, J=8.7, 5.5 Hz, 1H), 2.80 (ddd, J=14.2, 9.5, 5.2 Hz, 1H).

[0100] (2) By reference to the above method, corresponding C-glycoside compounds were respectively prepared by substituting glycosyl donor 1 with glycosyl donors 2-20.

Example 3: Preparation of Aryl C-Glycoside Compounds Using Sodium Sulfinate Glycosyl Donors as Raw Materials

##STR00093##

[0101] Aryl C-glycoside compounds were synthesized according to the above route, and the specific procedures were as follows: Glycosyl donor 1 (0.15 mmol), 4-methoxyiodobenzene (0.1 mmol), Ru(bpy).sub.3Cl.sub.2.Math.6H.sub.2O (0.8 mg, 1 mol %), NiBr.sub.2.Math.DME (3.1 mg, 10 mol %), diOMebpy (4,4-dimethoxy-2,2-bipyridine, 2.6 mg, 12 mol %), TMG (tetramethylguanidine, 12.5 L, 0.2 mmol) and DMSO (0.5 mL) were weighed, placed into a vial with a spiral cap and a magnetic stirring bar, and then mixed. The vial was filled with N.sub.2 and sealed with a Teflon cap. The mixture was stirred at room temperature under a 10 W, 455 nm LED light for 12 h, and then the reaction was completed.

[0102] The reaction solution was freeze-dried, and the residue was subjected to column chromatography (C.sub.18, H.sub.2O/MeCN=13:1), to obtain aryl C-glycoside as pure -configuration, with a yield of 67% and a purity of >98%. The structural characterization was as follows:

##STR00094##

[0103] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.25 (d, J=8.1 Hz, 2H), 6.86 (d, J=8.2 Hz, 2H), 4.98-4.83 (m, 2H), 4.70 (d, J=5.7 Hz, 1H), 4.42 (t, J=5.8 Hz, 1H), 3.95 (d, J=9.3 Hz, 1H), 3.82-3.59 (m, 4H), 3.44 (dt, J=11.8, 5.9 Hz, 1H), 3.30-3.08 (m, 4H); .sup.13C NMR (101 MHZ, DMSO-d.sub.6) 158.59, 132.50, 128.97, 113.07, 81.16, 81.04, 78.49, 74.67, 70.45, 61.48, 55.05; HRMS (DART-TOF) calculated for C.sub.13H.sub.18NaO.sub.6.sup.+ [M+Na].sup.+ m/z 293.0996, found 293.0995.

[0104] (2) By referring to the above method, corresponding aryl C-glycosides were respectively prepared by substituting glycosyl donor 1 with glycosyl donors 2-20.

Example 4: Preparation of S-Glycoside Compounds Using Sodium Sulfinate Glycosyl Donors as Raw Materials

##STR00095##

[0105] S-glycoside compounds were synthesized according to the above route, and the specific procedures were as follows: Glycosyl donor 1 (0.2 mmol), phenyl disulfide (0.3 mmol), Ru(bpy).sub.3Cl.sub.2.Math.6H.sub.2O (1 mol %), and DMSO (0.5 mL) were weighed, placed into a vial with a spiral cap and a magnetic stirring bar, and then mixed. The vial was filled with N.sub.2 and sealed with a Teflon cap. The mixture was stirred at room temperature under a 10 W, 455 nm LED light for 12 h, and then the reaction was completed.

[0106] The reaction solution was freeze-dried, and then subjected to column chromatography, to obtain the glycoside as pure -configuration, with a yield of 95% and a purity of >98%. The structural characterization was as follows:

##STR00096##

[0107] .sup.1H NMR (400 MHZ, DMSO-d.sub.6) 7.49 (d, J=7.1 Hz, 2H), 7.31 (t, J=7.4 Hz, 2H), 7.24 (t, J=7.3 Hz, 1H), 5.49 (d, J=5.3 Hz, 1H), 5.38 (d, J=4.3 Hz, 1H), 5.02 (d, J=5.4 Hz, 2H), 4.48 (t, J=5.9 Hz, 1H), 3.85 (ddd, J=10.0, 5.0, 2.3 Hz, 1H), 3.62-3.47 (m, 3H), 3.18 (dd, J=9.3, 5.5 Hz, 1H), 2.50 (t, J=1.9 Hz, 1H).

[0108] (2)

[0109] By referring to the above method, corresponding S-glycoside compounds were respectively prepared by substituting glycosyl donor 1 with glycosyl donors 2-20.

[0110] In summary, the present invention had provided a sulfinate glycosyl donor represented by formula I, and a method preparing the same, as well as the use of the sulfinate glycosyl donor represented by formula I in the preparation of glycosides such as S-glycosides and C-glycosides. The sulfinate glycosyl donor provided in the present invention had a novel structure containing a special sulfinate structure. The method for preparing the sulfinate glycosyl donor was simple, the reaction conditions were mild, and the yield was high, indicating the method was suitable for industrial production. If the sulfinate glycosyl donor of the present invention, as the raw material, was used to prepare glycosides, the addition of additional initiators was not required, that could save production costs, reduce by-products, and provide glycosides with a purity of >98%. The sulfinate glycosyl donor of the present invention had broad application prospects in the preparation of glycosides such as S-glycosides and C-glycosides (including aryl C-glycosides).