A method for preparing a silicon / germanium-glycoside compound

Abstract

This invention discloses a method for preparing silicon / germanium-glycoside compounds, belonging to the field of organic synthesis technology, comprising the following steps: adding a base, an olefin, a palladium catalyst, a ligand, a 5-haloenose, hexamethylsilyl (or hexamethylgerman), and an organic solvent sequentially to a dried reaction vessel, and reacting at 40-140°C for 6-36 hours; diluting the obtained material with ethyl acetate, then washing with water to separate the organic phase; drying, filtering, concentrating, and performing thin-layer chromatography or column chromatography to obtain the Si / Ge-glycoside compound. This invention can stereoselectively assemble various Si / Ge-glycoside compounds, with simple and safe procedures, and exhibits excellent chemoselectivity and broad functional group compatibility. This invention provides an efficient pathway for the development of Si / Ge-glycoside mimics with potential pharmaceutical activity and has important reference value for glycoside chemical modification and innovative drug development.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a method for preparing silicon / germanium-glycoside compounds. Background Art Glycosides are core structural units of natural products and drug molecules. Their glycosidic bond type and stereoconfiguration directly affect biological activity and metabolic stability, and are of great value in drug development. Traditional O-glycosides are easily hydrolyzed by enzymes, resulting in short half-lives and low bioavailability. Therefore, the development of heteroatom-modified sugar mimics has become a research hotspot in drug development and glycochemistry. Silicon and germanium atoms possess unique physicochemical properties, and their introduction into glycosides can significantly regulate molecular hydrophobicity, metabolic stability, and target binding ability. However, the efficient stereoselective synthesis of Si / Ge glycosides still faces two major obstacles: first, the larger atomic radii of Si and Ge atoms increase spatial repulsion with the sugar backbone, hindering bonding efficiency; second, the longer C-Si and C-Ge bonds make the stereochemical differentiation of anodic centers more complex. The existing synthesis of Si-glycosides mainly involves the use of glycosyl anions and silicon-based lithium reagents via a silicon-linked migration mechanism (Reference [1]: Pedretti, V., Veyrie' res, A., and Sinay¨, P. A novel 13 O→C silyl rearrangement in carbohydrate chemistry: Synthesis of α-D-glycopyranosyltrimethylsilanes. Tetrahedron 1990, 46, 77–88; Reference [2]: Shelar, SV, Davis, T., Ryan, N., Fisch, K., and Walczak, MA Si-Linked Glycomimetics through a Stereoselective SiliconTransfer and Anion Addition. J. Am. Chem. Soc. 2024, 146, 29285–29291.); while the synthesis of Ge-glycosides is mainly achieved through the decarboxylation coupling of nickel-catalyzed redox active esters with germanium-based zinc reagents (Reference [3]: Wang et al., Stereoselective C(sp3)-Si / Ge bond formation via nickel-catalyzed decarboxylative couplings, Chem, 2025, DOI:10.1016 / j.chempr.2025.102713). However, the above methods mostly rely on harsh conditions such as low-temperature lithiation, silicon-based migration, and germanium-based zinc reagents, resulting in many side reactions and low yields, which may also lead to limitations in operability and scalability. Therefore, this unmet need highlights the importance of developing innovative methods to assemble Si- and Ge-linked glycosimulants.

[0002] Palladium-catalyzed Catellani reactions offer advantages such as modularity and high regioselectivity. 5-Iodoenoses serve as key building blocks, enabling the synthesis of C-glycosides via ortho-carbon bond formation through palladium-catalyzed Catellani reactions. However, existing methods have significant limitations: they are limited to a single reaction type and struggle to link Group 14 elements such as silicon and germanium to the sugar backbone.

[0003] In summary, existing glycoside synthesis technologies struggle to simultaneously achieve structural diversity, high stereoselectivity, atom economy, and mild reaction conditions, failing to meet the demands of novel glycoside drug development for structurally unique and high-performance glycoside derivatives. Therefore, developing a Si / Ge-glycoside catalytic assembly method that requires no additional directing groups, operates under mild reaction conditions, and exhibits high stereoselectivity has become a critical technological challenge urgently needing breakthroughs in carbohydrate chemistry and drug synthesis. Summary of the Invention

[0004] The purpose of this invention is to overcome the harsh conditions that glycoside compounds rely on, such as low-temperature lithiation, silicon-based migration, and germanium-zinc reagents, and to provide a method for preparing silicon / germanium-glycoside compounds that does not require additional directing groups, has mild reaction conditions, and high stereoselectivity.

[0005] The technical solution of the present invention is as follows: A method for preparing a silicon / germanium-glycoside compound includes the following steps: (1) Add base, olefin, palladium catalyst, ligand, 5-halogenated enose, hexamethylsilyl (or hexamethylgerman) and organic solvent sequentially to a high-temperature dry reaction vessel, and react at 50~100℃ for 15~30h; The molar ratio of 5-haloenose, hexamethylsilyl (or hexamethylgermanane), olefin, palladium catalyst, ligand and base is 0.8~1.2:1.0~3.0:1.0~3.0:0.08~0.12:0.18~0.22:1.0~3.0, and the organic solvent corresponding to each mole of 5-iodoenose is 1~3L; (2) The material obtained in step (1) is diluted with ethyl acetate and then washed with water to separate the organic phase; (3) The organic phase obtained in step (2) is dried, filtered, concentrated, and subjected to thin-layer chromatography or column chromatography to obtain the Si / Ge-glycoside derivative; The structural formula of the 5-halogenated enose is: Where X is a halogen and P is hydrogen, alkyl, alkoxy, acyl, aryl, or benzyl; The structural formula of the olefin is as follows: Where Y is C, O, or N, R1 is hydrogen, alkyl, acyl, aryl, carboxylic acid, ester, amide, sulfonyl, or trifluoromethyl, and R2 is hydrogen, alkyl, aryl, acyl, carboxylic acid, ester, amide, sulfonyl, or trifluoromethyl.

[0006] Preferably, the palladium catalyst is palladium acetate, palladium trifluoroacetate, palladium dichloride, bis(triphenylphosphine)dichloride, bis(acetonitrile)dichloride, palladium acetylacetonate, palladium diacetylacetonate, palladium diacetylacetonate, allyl palladium chloride dimer, tetra(triphenylphosphine)palladium, [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride, or tris(dibenzylacetone)dipalladium. The ligands are triphenylphosphine, tris(2-furanyl)phosphine, 2-dicyclohexylphosphine-2',6'-diisopropoxy-1,1'-biphenyl, trinaphthylphosphine, 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl, 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl, tricyclohexylphosphine, 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, pyridine, bipyridine, 2-hydroxy-3-trifluoromethylpyridine, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 1,1'-bis(diphenylphosphine)ferrocene, or 1,1'-bi-2-naphthol; The base is sodium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, sodium carbonate, sodium phosphate, potassium carbonate, potassium phosphate, potassium dihydrogen phosphate, cesium carbonate, cesium acetate, cesium hydroxide, or 1,8-diazabicycloundec-7-ene. The organic solvent is dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexafluoroisopropanol, 1,2-dichloroethane, toluene, 1,4-dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether, polyethylene glycol dimethyl ether, or ethylene glycol diethyl ether.

[0007] Preferably, the halogen is fluorine, iodine, chlorine, or bromine.

[0008] Preferably, the palladium catalyst is palladium acetate, the ligand is tris(2-furanyl)phosphine, the base is cesium carbonate, and the organic solvent is acetonitrile or N-methylpyrrolidone.

[0009] Preferably, the reaction temperature in step (1) is 60~80℃.

[0010] Preferably, the reaction time in step (1) is 24 hours.

[0011] Preferably, the molar ratio of the 5-haloenose, hexamethylsilyl (or hexamethylgermanane), olefin, palladium catalyst, ligand and base is 1:2:2:0.1:0.2:2, and the organic solvent corresponding to each mole of 5-haloenose is 1~2L.

[0012] The beneficial effects of this invention are: 1. This invention can simultaneously obtain Si / Ge-glycoside compounds with different functional group substitutions, and has good stereoselectivity, enabling the synthesis of Si / Ge-glycoside derivatives that are not easily obtained by other methods; 2. The method of the present invention has high yield, mild reaction conditions, simple operation steps, wide substrate range, and simple and green post-processing. Detailed Implementation

[0013] The technical solution of the present invention will be further explained and described below through specific embodiments. Example 1 Preparation of ((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((1R,4S)-3-(trimethylsilyl)bicyclo[2.2.1]heptane-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0014] 0.2 mmol of cesium carbonate, 0.2 mmol of norbornene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 59.1 mg of the target product, with a yield of 91%. The NMR characterization of the compound is as follows: 1H NMR(400 MHz, Chloroform-d) δ 7.43 – 7.22 (m, 10H), 7.22 – 7.18 (m, 3H), 7.09(dd,J= 6.7, 2.9 Hz, 2H), 4.66 (d,J= 12.4 Hz, 1H), 4.58 – 4.48 (m, 2H), 4.48 –4.32 (m, 3H), 4.30 – 4.26 (m, 1H), 3.96 (s, 1H), 3.82 (t,J= 2.6 Hz, 1H), 3.72(dd,J= 10.5, 7.3 Hz, 1H), 3.40 (dd,J= 10.5, 4.5 Hz, 1H), 2.84 (d,J= 10.8 Hz,1H), 2.16 (d,J= 15.7, 2H), 1.65 – 1.56 (m, 2H), 1.47 – 1.40 (m, 1H), 1.31 –1.23 (m, 2H), 1.16 (d,J= 9.1, 1H), 1.04 (d,J= 10.8, 1H), 0.23 (s, 9H), -0.11(s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 156.95, 138.43, 138.35, 128.35,128.25, 128.04, 127.58, 127.52, 127.40, 127.17, 121.06, 74.12, 73.11, 71.52,71.16, 70.61, 70.47, 70.01, 48.41, 41.34, 41.01, 39.22, 37.81, 33.22, 31.47,0.19, 0.03. Example 2: Preparation of ((2S,3R,4S)-3,4-di(benzyloxy)-2-(benzyloxymethyl)-5-((1R,4R)-3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4-epoxynaphthyl-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0015] 0.2 mmol of cesium carbonate, 0.2 mmol of (1R,4S)-1,4-dihydro-1,4-oxanaphthalene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 43 mg of the target product, with a yield of 61%. The NMR characterization of the compound is as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.40 – 7.10 (m, 19H), 5.26 (d,J= 7.9Hz, 2H), 4.70 (d,J= 12.3 Hz, 1H), 4.65 – 4.42 (m, 5H), 4.33 – 4.19 (m, 2H), 4.06 (t,J= 2.7 Hz, 1H), 3.77 (dd,J= 10.2, 6.9 Hz, 1H), 3.59 (dd,J= 10.2, 5.4Hz, 1H), 2.96 (d,J= 10.1 Hz, 1H), 1.10 (d,J= 10.1 Hz, 1H), 0.11 (s, 9H), 0.04 (s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 159.36, 148.85, 144.88, 138.86,138.45, 138.28, 134.41, 128.37, 128.27, 127.97, 127.59, 127.57, 127.48,127.37, 126.98, 126.88, 126.41, 125.88, 122.42, 118.76, 117.09, 83.04, 80.73,75.63, 73.14, 72.81, 70.87, 70.82, 70.64, 70.32, 45.71, 35.57, -0.05, -0.41. Example 3: Preparation of (3aS,4S,7R,7aS)-5-((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-6-(trimethylsilyl)-3,4-dihydro-2H-pyran-5-yl)-2-(2,2,2-trifluoroethyl)-6-(trimethylsilyl)hexahydro-1H-4,7-methylene isondecan-1,3(2H)-dione

[0016] 0.2 mmol of cesium carbonate, 0.2 mmol of (3aR,4S,7R,7aS)-2-(2,2,2-trifluoroethyl)-3a,4,7,7a-tetrahydro-1H-4,7-methyleneisoinden-1,3(2H)-dione, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 61.7 g / L. mg of the target product was obtained, with a yield of 77%. The NMR characterization of this compound is as follows: 1H NMR (400MHz, Chloroform-d) δ 7.42 – 7.34 (m, 2H), 7.35 – 7.21 (m, 6H), 7.25 – 7.19(m, 5H), 7.11 – 7.02 (m, 2H), 4.68 (d,J= 12.5 Hz, 1H), 4.49 (d,J= 12.5 Hz,1H), 4.46 – 4.35 (m, 4H), 4.35 – 4.31 (m, 1H), 4.14 – 4.07 (m, 2H), 3.90 (t,J= 2.5 Hz, 1H), 3.82 (t,J= 2.3 Hz, 1H), 3.66 (dd,J= 10.4, 7.2 Hz, 1H), 3.42(dd,J= 10.4, 5.0 Hz, 1H), 3.29 – 3.21 (m, 2H), 2.79 (dd,J= 10.8, 1.5 Hz, 1H),2.71 (d,J= 4.9 Hz, 1H), 2.63 (dd,J= 4.2, 1.8 Hz, 1H), 1.90 (d,J= 9.7 Hz, 1H),1.54 (d,J= 9.7 Hz, 1H), 0.94 (dd,J= 10.8, 1.7 Hz, 1H), 0.14 (s, 9H), -0.12(s, 9H); 19 F NMR (376 MHz, Chloroform-d) δ -69.78; 13 C NMR (101 MHz, Chloroform-d) δ 176.44, 176.37, 159.11, 138.24, 138.16, 137.45, 128.45, 128.24, 128.14,127.97, 127.63, 127.54, 127.46, 127.43, 122.92 (q,J= 280.0 Hz), 118.33,73.67, 73.09, 70.98, 70.58, 70.43, 70.36, 69.47, 51.05, 49.56, 43.45, 42.84,41.63, 41.54, 39.17 (q,J= 36.5 Hz), 35.43, -0.31, -0.48. Example 4: Preparation of 2-((3aS,4S,7R,7aS)-5-((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-6-(trimethylsilyl)-3,4-dihydro-2H-pyran-5-yl)-1,3-dioxo-6-(trimethylsilyl)octahydro-2H-4,7-methaneisoindolin-2-yl)acetonitrile)

[0017] 0.2 mmol of cesium carbonate, 0.2 mmol of 2-((3aR,4S,7R,7aS)-1,3-dioxo-1,3,3a,4,7,7a-hexahydro-2H-4,7-methyleneisoindolidin-2-yl)acetonitrile, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of 5-iodoenose, 0.2 mmol of hexamethylsilyl ether, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 68.6 mg of the target product, with a yield of 90%. The NMR characterization of the compound is as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.42 – 7.38 (m, 2H), 7.35 – 7.21 (m,11H), 7.07 (dd,J= 6.4, 3.2 Hz, 2H), 4.70 (d,J= 12.5 Hz, 1H), 4.52 – 4.28 (m,8H), 3.92 (t,J= 2.4 Hz, 1H), 3.82 (t,J= 2.3 Hz, 1H), 3.67 (dd,J= 10.4, 7.3Hz, 1H), 3.42 (dd,J= 10.3, 5.0 Hz, 1H), 3.30 – 3.22 (m, 2H), 2.81 (d,J= 10.7Hz, 1H), 2.73 (d,J= 5.0 Hz, 1H), 2.67 (d,J= 4.0 Hz, 1H), 1.91 (d,J= 9.8 Hz,1H), 1.57 (s, 1H), 0.92 (dd,J= 10.7, 2.0 Hz, 1H), 0.15 (s, 9H), -0.10 (s,9H); 13C NMR (101 MHz, Chloroform-d) δ 175.79, 175.74, 159.22, 138.24, 138.15,137.41, 128.48, 128.28, 128.18, 128.00, 127.68, 127.59, 127.50, 118.24,113.08, 73.61, 73.13, 70.95, 70.57, 70.43, 70.22, 69.48, 51.32, 49.81, 43.61,43.03, 41.70, 41.66, 35.59, 25.50, -0.29, -0.33. Example 5: Preparation of (3aS,4S,7R,7aS)-2-benzyl-5-((2S,3R,4S)-3,4-bis(benzyloxy)-2-((benzyloxy)methyl)-6-(trimethylsilyl)-3,4-dihydro-2H-pyran-5-yl)-6-(trimethylsilyl)hexahydro-1H-4,7-methyleneisoindidine-1,3(2H)-dione

[0018] 0.2 mmol of cesium carbonate, 0.2 mmol of (3aR,4S,7R,7aS)-2-benzyl-3a,4,7,7a-tetrahydro-1H-4,7-methyleneisoindoline-1,3(2H)-dione, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na2SO4, filtered, concentrated, and purified by thin-layer chromatography to obtain 63.7 mg of the target product, with a yield of 78%. The NMR characterization of this compound is as follows: 1H NMR (400 MHz, Chloroform-d) δ 7.48 – 7.40 (m, 4H), 7.40 – 7.29 (m, 11H), 7.27 – 7.24 (m, 3H), 7.12(dd,J= 6.7, 3.0 Hz, 2H), 4.76 – 4.61 (m, 3H), 4.54 (d,J= 12.5 Hz, 1H), 4.51 –4.41 (m, 4H), 4.39 – 4.36 (m, 1H), 3.95 (s, 1H), 3.89 (s, 1H), 3.73 (dd,J=10.4, 7.2 Hz, 1H), 3.49 (dd,J= 10.4, 4.9 Hz, 1H), 3.18 – 3.08 (m, 2H), 2.97 –2.87 (m, 1H), 2.75 (d,J= 5.2 Hz, 1H), 2.66 (d,J= 4.5 Hz, 1H), 1.93 (d,J= 9.6Hz, 1H), 1.55 (d,J= 9.9 Hz, 1H), 1.11 (dd,J= 10.8, 1.9 Hz, 1H), 0.24 (s, 9H),-0.04 (s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 177.71, 177.47, 159.07,138.27, 138.20, 137.57, 135.92, 129.02, 128.98, 128.50, 128.43, 128.23,128.17, 128.11, 127.91, 127.83, 127.59, 127.45, 127.42, 118.55, 73.73, 73.07,71.11, 70.57, 70.51, 70.44, 69.54, 51.08, 49.68, 43.35, 42.93, 42.14, 41.61, 41.54, 35.36, -0.21, -0.44. Example 6: Preparation of methyl 2-((3aS,4S,7R,7aS)-5-((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-6-(trimethylsilyl)-3,4-dihydro-2H-pyran-5-yl)-1,3-dioxo-6-(trimethylsilyl)octahydro-2H-4,7-methylthiobridged isoxaloline-2-yl)acetate

[0019] 0.2 mmol of cesium carbonate, 0.2 mmol of methyl 2-((3aR,4S,7R,7aS)-1,3-dione-1,3,3a,4,7,7a-hexahydro-2H-4,7-methaneisoindolid-2-yl)acetate, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilyl, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na2SO4, filtered, concentrated, and purified by thin-layer chromatography to obtain 40.7 mg of the target product, with a yield of 51%. The NMR characterization of this compound is as follows: 1 H NMR (400MHz, Chloroform-d) δ 7.43 – 7.37 (m, 2H), 7.36 – 7.21 (m, 11H), 7.13 – 7.03(m, 2H), 4.70 (d,J= 12.5 Hz, 1H), 4.54 – 4.32 (m, 6H), 3.91 (t,J= 2.4 Hz,1H), 3.85 (t,J= 2.3 Hz, 1H), 3.76 (s, 3H), 3.68 (dd,J= 10.4, 7.2 Hz, 1H), 3.44 (dd,J= 10.4, 5.0 Hz, 1H), 3.32 – 3.24 (m, 2H), 2.83 (dd,J= 10.8, 1.5 Hz,1H), 2.73 (d,J= 5.1 Hz, 1H), 2.66 (d,J= 4.4 Hz, 1H), 1.91 (d,J= 9.8 Hz, 1H), 1.57 (d,J= 10.0 Hz, 1H), 1.02 (dd,J= 10.8, 2.0 Hz, 1H), 0.16 (s, 9H), -0.10(s, 9H); 13C NMR (101 MHz, Chloroform-d) δ 177.05, 177.00, 167.07, 159.03,138.26, 138.19, 137.54, 128.44, 128.24, 128.13, 127.94, 127.63, 127.50,127.48, 127.46, 127.45, 118.51, 73.70, 73.08, 71.07, 70.58, 70.41, 69.52,52.61, 51.26, 49.83, 43.48, 42.96, 41.68, 39.11, 35.38, -0.25, -0.46. Example 7: Preparation of (3aS,4S,7R,7aS)-2-allyl-5-((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxymethyl)-6-(trimethylsilyl)-3,4-dihydro-2H-pyran-5-yl)-6-(trimethylsilyl)hexylhydro-1H-4,7-methyleneisoindidine-1,3(2H)-dione

[0020] 0.2 mmol of cesium carbonate, 0.2 mmol of (3aR,4S,7R,7aS)-2-allyl-3a,4,7,7a-tetrahydro-1H-4,7-methyleneisocampheneimidazole-1,3(2H)-dione, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na2SO4, filtered, concentrated, and purified by thin-layer chromatography to obtain 58.4 mg of the target product, with a yield of 77%. The NMR characterization of this compound is as follows: 1H NMR (400 MHz, Chloroform-d) δ 7.44 – 7.38 (m, 2H), 7.37 – 7.22 (m, 11H), 7.14 – 7.06 (m,2H), 5.87 – 5.78 (m, 6.0 Hz, 1H), 5.28 (dd,J= 17.1, 1.4 Hz, 1H), 5.21 (dd,J=10.2, 1.3 Hz, 1H), 4.71 (d,J= 12.5 Hz, 1H), 4.56 – 4.32 (m, 6H), 4.17 – 4.07(m, 2H), 3.92 (t,J= 2.5 Hz, 1H), 3.87 (t,J= 2.3 Hz, 1H), 3.70 (dd,J= 10.4,7.2 Hz, 1H), 3.45 (dd,J= 10.4, 4.9 Hz, 1H), 3.23 – 3.13 (m, 2H), 2.85 (dd,J=10.8, 1.5 Hz, 1H), 2.73 (d,J= 5.1 Hz, 1H), 2.65 (d,J= 4.4 Hz, 1H), 1.91 (d,J=8.6 Hz, 1H), 1.56 (d,J= 9.6 Hz, 1H), 1.05 (dd,J= 10.8, 1.7 Hz, 1H), 0.20 (s,9H), -0.08 (s,9H); 13 C NMR (101 MHz, Chloroform-d) δ 177.58, 177.40, 159.03,138.25, 138.18, 137.56, 130.80, 128.42, 128.21, 128.10, 127.88, 127.59,127.46, 127.44, 127.41, 118.49, 118.46, 73.67, 73.05, 71.03, 70.53, 70.38,70.36, 69.54, 51.04, 49.62, 43.40, 42.90, 41.63, 41.57, 40.76, 35.25, -0.24, -0.42. Example 8: Preparation of ((2S,3R,4S)-3,4-di(benzoxy)-2-((benzoxy)methyl)-5-((1S,4R,5S,8R)-3-(trimethylsilyl)decahydro-1,4:5,8-dimethylenenaphthal-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0021] 0.2 mmol of cesium carbonate, 0.2 mmol of (1R,4S,5S,8R)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethylenenaphthalene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 40.6 mg of the target product, with a yield of 56%. The NMR characterization of the compound is as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.39 –7.19 (m, 13H), 7.09 (dd,J= 6.6, 2.9 Hz, 2H), 4.68 (d,J= 12.6 Hz, 1H), 4.59 –4.29 (m, 6H), 3.95 (d,J= 2.3 Hz, 1H), 3.84 (d,J= 2.3 Hz, 1H), 3.72 (dd,J=10.5, 7.6 Hz, 1H), 3.38 (dd,J= 10.5, 4.6 Hz, 1H), 3.07 – 2.92 (m, 1H), 2.24 –2.09 (m, 3H), 2.09 – 2.02 (m, 1H), 1.88 – 1.68 (m, 3H), 1.54 – 1.38 (m, 4H), 1.29 – 1.25 (m, 1H), 1.02 (t,J= 10.7 Hz, 3H), 0.27 (s, 9H), -0.11 (s, 9H); 13CNMR (101 MHz, Chloroform-d) δ 157.49, 138.53, 138.47, 138.33, 128.37, 128.24,128.04, 127.58, 127.46, 127.38, 127.14, 121.24, 74.14, 73.02, 70.56, 70.50,70.39, 70.27, 70.23, 51.67, 51.40, 46.41, 43.58, 41.71, 41.10, 36.46, 36.08,34.43, 32.47, 31.51, 31.36, 0.27, -0.20. Example 9: Preparation of ((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((1S,4R)-5,8-dimethyl-3-(trimethylsilyl)-1,2,3,4,4a,8b-hexahydro-1,4-methylenebisbenzocyclopenten-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0022] 0.2 mmol of cesium carbonate, 0.2 mmol of (1R,4S)-5,8-dimethyl-1,4,4a,8b-tetrahydro-1,4-methylenebiphenyl, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 57 mg of the target product, with a yield of 75%. The NMR characterization of the compound is as follows: 1H NMR (400 MHz, Chloroform-d) δ 7.42 – 7.29 (m, 10H), 7.26 – 7.22 (m, 3H), 7.15 – 7.08 (m, 2H), 6.95 (s, 2H), 4.74 (d,J= 12.4 Hz,1H), 4.61 – 4.36 (m, 6H), 3.99 (t,J= 2.3 Hz, 1H), 3.92 (t,J= 2.6 Hz, 1H), 3.79 (dd,J= 10.5, 7.3 Hz, 1H), 3.50 (dd,J= 10.4, 4.7 Hz, 1H), 3.24 (s, 2H),2.91 (d,J= 10.7 Hz, 1H), 2.30 (s, 1H), 2.23 (s, 1H), 2.20 (s, 6H), 1.33 (d,J=9.8 Hz, 1H), 1.05 (dd,J= 10.7, 2.0 Hz, 1H), 0.91 (d,J= 9.8 Hz, 1H), 0.35 (s,9H), -0.01 (s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 157.58, 144.81, 143.85,138.36, 138.28, 138.18, 129.24, 128.83, 128.35, 128.28, 128.25, 128.03,127.63, 127.58, 127.52, 127.48, 127.42, 127.21, 120.69, 74.01, 73.12, 71.90,71.20, 70.71, 70.48, 69.87, 52.00, 50.16, 46.66, 40.16, 39.06, 38.68, 31.36, 16.43, 16.22, 0.22, 0.10. Example 10: Preparation of ((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((9S,12R)-11-(trimethylsilyl)-8c,9,10,11,12,12a-hexahydro-9,12-methylenebenzo[3,4]cyclobutano[1,2-l]phenanthranil-10-yl)-3,4-dihydro-2H-furan-6-yl)trimethylsilane

[0023] 0.2 mmol of cesium carbonate, 0.2 mmol of (9R,12S)-8c,9,12,12a-tetrahydro-9,12-methylenebenzo[3,4]cyclobut[1,2-l]phenanthrene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na2SO4, filtered, concentrated, and purified by thin-layer chromatography to obtain 64.4 mg of the target product, with a yield of 78%. The NMR characterization of the compound is as follows: 1 H NMR (400 MHz, Chloroform-d) δ 8.81 –8.78 (m, 2H), 7.88 – 7.84 (m, 2H), 7.69 – 7.62 (m, 4H), 7.46 – 7.31 (m, 10H),7.23 – 7.18 (m, 3H), 7.06 (dd,J= 6.6, 2.9 Hz, 2H), 4.78 (d,J= 12.5 Hz, 1H), 4.64 – 4.32 (m, 6H), 3.99 (d,J= 2.3 Hz, 1H), 3.92 (t,J= 2.4 Hz, 1H), 3.82(dd,J= 10.4, 7.3 Hz, 1H), 3.61 (s, 2H), 3.52 (dd,J= 10.4, 4.8 Hz, 1H), 3.09(d,J= 10.6 Hz, 1H), 2.47 (s, 1H), 2.42 (s, 1H), 1.37 – 1.30 (m, 1H), 1.23(dd,J= 10.7, 2.0 Hz, 1H), 0.90 (d,J= 10.1 Hz, 1H), 0.43 (s, 9H), 0.04 (s,9H); 13C NMR (101 MHz, Chloroform-d) δ 157.63, 140.77, 139.67, 138.34, 138.32,138.01, 130.77, 130.74, 128.37, 128.27, 128.25, 128.13, 128.00, 127.61,127.52, 127.47, 127.43, 127.21, 126.53, 126.48, 125.60, 125.54, 123.79,123.75, 123.14, 122.85, 120.47, 73.92, 73.11, 71.68, 70.92, 70.69, 70.39, 69.85, 52.18, 50.34, 47.10, 39.67, 39.43, 38.16, 31.18, 0.23, 0.17. Example 11: Preparation of ((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((1S,4R)-3-(trimethylsilyl)bicyclo[2.2.1]hept-5-en-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0024] 0.2 mmol of cesium carbonate, 0.2 mmol of norbornene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 20.2 mg of the target product, with a yield of 31%. The NMR characterization of the compound is as follows: 1H NMR (400MHz, Chloroform-d) δ 7.40 – 7.20 (m, 13H), 7.08 (dd,J= 6.6, 2.9 Hz, 2H), 6.16– 6.12 (m, 2H), 4.71 (d,J= 12.5 Hz, 1H), 4.56 (d,J= 12.5 Hz, 1H), 4.49 – 4.29(m, 5H), 3.93 – 3.82 (m, 2H), 3.75 (dd,J= 10.5, 7.5 Hz, 1H), 3.42 (dd,J=10.5, 4.6 Hz, 1H), 2.84 – 2.74 (m, 1H), 2.65 (dd,J= 10.3, 1.5 Hz, 2H), 1.41 –1.32 (m, 2H), 0.77 (dd,J= 10.5, 1.9 Hz, 1H), 0.20 (s, 9H), -0.07 (s, 9H); 13 CNMR (101 MHz, Chloroform-d) δ 157.63, 138.69, 138.38, 138.20, 135.49, 128.39,128.26, 128.05, 127.65, 127.57, 127.52, 127.41, 127.19, 119.19, 73.88, 73.11,71.01, 70.55, 70.39, 70.28, 70.13, 46.82, 46.57, 44.17, 32.21, -0.13, -0.15. Example 12: Preparation of (1R,4R)-2-((2S,3R,4S)-3,4-bis(benzyloxy)-2-((benzyloxy)methyl)-6-(trimethylsilyl)-3,4-dihydro-2H-pyran-5-yl)-9-toluenesulfonyl-3-(trimethylsilyl)-1,2,3,4-tetrahydro-1,4-iminonaphthalene

[0025] 0.2 mmol of cesium carbonate, 0.2 mmol of (1R,4S)-9-toluenesulfonyl-1,4-dihydro-1,4-iminonaphthalene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 41.2 mg of the target product, with a yield of 48%. The NMR characterization of the compound is as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.57 (d,J= 7.0 Hz, 2H), 7.49 (t,J= 7.5 Hz, 2H), 7.44 – 7.40 (m, 1H), 7.38 – 7.26 (m, 10H), 7.10 (d,J=8.0 Hz, 2H), 6.85 – 6.73 (m, 5H), 6.66 (d,J= 7.2 Hz, 1H), 5.05 – 4.86 (m,4H), 4.80 – 4.70 (m, 3H), 4.47 (s, 2H), 4.43 – 4.37 (m, 1H), 4.10 (s, 1H),3.85 (dd,J= 10.3, 7.6 Hz, 1H), 3.53 (dd,J= 10.3, 5.0 Hz, 1H), 2.85 (d,J= 10.2Hz, 1H), 2.23 (s, 3H), 1.01 (d,J= 10.2 Hz, 1H), 0.15 (s, 9H), 0.10 (s, 9H); 13CNMR (101 MHz, Chloroform-d) δ 159.47, 145.40, 142.50, 142.38, 139.18, 138.95,138.32, 134.32, 128.60, 128.36, 128.23, 127.97, 127.88, 127.51, 127.41,127.30, 127.02, 126.90, 126.66, 126.22, 125.62, 120.41, 119.68, 118.30,76.22, 72.99, 71.18, 70.86, 70.21, 70.12, 68.18, 68.02, 65.58, 46.59, 36.69, 21.27, -0.29, -0.53. Example 13: Preparation of ((2S,3R,4S)-3,4-dimethoxy-2-(methoxymethyl)-5-((1R,4S)-3-(trimethylsilyl)bicyclo[2.2.1]hept-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0026] 0.2 mmol of cesium carbonate, 0.2 mmol of norbornene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-5-iodo-3,4-dimethoxy-2-(methoxymethyl)-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylene, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 22.9 mg of the target product, with a yield of 54%. The NMR characterization of the compound is as follows: 1H NMR (400 MHz, Chloroform-d) δ 4.13 – 4.08 (m, 1H), 3.68 (t,J= 2.3 Hz, 1H), 3.63 (t,J= 3.5Hz, 1H), 3.59 (dd,J= 6.1, 2.6 Hz, 2H), 3.42 (s, 3H), 3.35 (s, 3H), 3.30 (s,3H), 2.74 (d,J= 10.8 Hz, 1H), 2.20 (d,J= 3.7 Hz, 1H), 2.07 (d,J= 3.8 Hz, 1H),1.64 – 1.54 (m, 2H), 1.39 (d,J= 9.6 Hz, 1H), 1.26 – 1.21 (m, 2H), 1.13 (d,J=9.2 Hz, 1H), 1.01 (dd,J= 10.8, 1.9 Hz, 1H), 0.17 (s, 9H), -0.03 (s, 9H); 13 CNMR (101 MHz, Chloroform-d) δ 155.72, 121.85, 73.40, 73.37, 72.59, 71.22,58.96, 57.22, 55.45, 48.16, 41.48, 41.30, 39.26, 37.36, 33.18, 31.58, 0.23, -0.08. Example 14: Preparation of ((2S,3R,4S)-3,4-diethoxy-2-(ethoxymethyl)-5-((1R,4S)-3-(trimethylsilyl)bicyclo[2.2.1]hept-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0027] 0.2 mmol of cesium carbonate, 0.2 mmol of norbornene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-5-iodo-3,4-diethoxy-2-(ethoxymethyl)-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 20.9 mg of the target product, with a yield of 45%. The NMR characterization of the compound is as follows: 1H NMR (400 MHz,Chloroform-d) δ 4.16 – 4.10 (m, 1H), 3.74 (t,J= 2.4 Hz, 1H), 3.69 – 3.47 (m,10H), 2.82 – 2.72 (m, 1H), 2.23 – 2.19 (m, 1H), 2.10 (d,J= 3.6 Hz, 1H), 1.62– 1.58 (m, 1H), 1.47 (d,J= 9.1 Hz, 1H), 1.26 – 1.22 (m, 2H), 1.20 – 1.13 (m,10H), 1.02 (dd,J= 10.8, 1.9 Hz, 1H), 0.17 (s, 9H), 0.00 (s, 9H); 13 C NMR (101MHz, Chloroform-d) δ 156.30, 121.86, 74.49, 71.84, 70.53, 69.81, 66.52,64.35, 63.25, 48.32, 41.52, 40.91, 39.18, 37.68, 33.30, 31.52, 15.59, 15.45,15.27, 0.27, -0.04. Example 15: Preparation of ((2R,3R,4R)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((1R,4S)-3-(trimethylsilyl)bicyclo[2.2.1]hept-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0028] 0.2 mmol of cesium carbonate, 0.2 mmol of norbornene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2S,3R,4R)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 29.7 mg of the target product, with a yield of 45%. The NMR characterization of the compound is as follows: 1H NMR (400MHz, Chloroform-d) δ 7.36 – 7.27 (m, 10H), 7.25 – 7.16 (m, 5H), 5.06 (d,J=11.6 Hz, 1H), 4.65 (s, 2H), 4.57 (d,J= 11.6 Hz, 1H), 4.50 (d,J= 6.7 Hz, 2H), 4.39 – 4.35 (m, 1H), 4.29 – 4.23 (m, 1H), 3.99 (dd,J= 11.1, 8.0 Hz, 1H), 3.87 (dd,J= 5.1, 3.1 Hz, 1H), 3.80 (dd,J= 11.0, 2.6 Hz, 1H), 2.73 (d,J= 11.0 Hz,1H), 2.19 – 2.13 (m, 1H), 2.05 (d,J= 3.4 Hz, 1H), 1.65 – 1.59 (m, 2H), 1.53(d,J= 9.2 Hz, 1H), 1.25 – 1.17 (m, 3H), 1.03 (dd,J= 10.9, 1.9 Hz, 1H), 0.21(s, 9H), -0.14 (s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 155.88, 138.75,138.66, 138.25, 128.28, 127.84, 127.82, 127.63, 127.53, 127.39, 126.86,121.68, 73.90, 73.18, 72.94, 72.22, 70.60, 69.75, 47.93, 41.64, 40.98, 38.92,38.22, 33.14, 31.61, 0.05, 0.02. Example 16: Preparation of ((2S,3R,4S)-3,4-di(benzoxy)-2-((benzoxy)methyl)-5-((1R,4S)-3-(trimethylgermanium)bicyclo[2.2.1]hept-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylgermanane

[0029] 0.2 mmol of cesium carbonate, 0.2 mmol of norbornene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylgermanane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 43.6 mg of the target product, with a yield of 58%. The NMR characterization of the compound is as follows: 1 H NMR (400MHz, Chloroform-d) δ 7.40 – 7.28 (m, 10H), 7.26 – 7.21 (m, 3H), 7.13 (dd,J=6.7, 2.9 Hz, 2H), 4.71 (d,J= 12.4 Hz, 1H), 4.59 – 4.52 (m, 2H), 4.52 – 4.42(s, 2H), 4.39 (d,J= 12.2 Hz, 1H), 4.35 – 4.32 (m, 1H), 4.01 (t,J= 2.4 Hz,1H), 3.85 (t,J= 2.7 Hz, 1H), 3.78 (dd,J= 10.5, 7.3 Hz, 1H), 3.46 (dd,J= 10.6,4.5 Hz, 1H), 2.77 (d,J= 10.5 Hz, 1H), 2.19 (t,J= 4.1 Hz, 2H), 1.67 – 1.62 (m,2H), 1.49 (d,J= 9.2 Hz, 1H), 1.31 – 1.27 (m, 3H), 1.20 (dt,J= 9.2 Hz, 1H), 0.40 (s, 9H), 0.03 (s, 9H); 13C NMR (101 MHz, Chloroform-d) δ 159.27, 138.44,138.40, 138.36, 128.36, 128.24, 128.05, 127.67, 127.60, 127.54, 127.47,127.39, 127.23, 118.30, 74.52, 73.07, 71.82, 71.06, 70.91, 70.58, 69.83,49.33, 43.58, 40.83, 39.79, 37.42, 32.96, 31.30, -0.09, -0.15. Example 17: Preparation of ((2R,3R,4R)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((1R,4S)-3-(trimethylgermanium)bicyclo[2.2.1]hept-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylgermanane

[0030] 0.2 mmol of cesium carbonate, 0.2 mmol of norbornene, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2S,3R,4R)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylgermanane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 46.9 mg of the target product, with a yield of 63%. The NMR characterization of the compound is as follows: 1H NMR (400MHz, Chloroform-d) δ 7.38 – 7.30 (m, 11H), 7.27 – 7.21 (m, 4H), 5.09 (d,J=11.4 Hz, 1H), 4.68 (s, 2H), 4.57 (dd,J= 19.0, 11.3 Hz, 3H), 4.47 – 4.40 (m,1H), 4.29 (d,J= 1.9 Hz, 1H), 4.10 – 4.05 (m, 1H), 3.92 (dd,J= 5.3, 3.1 Hz,1H), 3.85 (dd,J= 11.1, 2.3 Hz, 1H), 2.66 (d,J= 10.5 Hz, 1H), 2.14 (d,J= 16.6Hz, 2H), 1.68 – 1.62 (m, 2H), 1.55 (d,J= 9.4 Hz, 1H), 1.28 – 1.22 (m, 4H), 0.37 (s, 9H), -0.00 (s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 158.43, 138.81,138.70, 138.15, 128.29, 128.27, 127.84, 127.81, 127.57, 127.55, 127.38,127.35, 126.86, 119.22, 74.30, 73.18, 73.13, 72.10, 70.43, 69.60, 48.80,43.68, 40.88, 39.49, 37.79, 32.92, 31.29, -0.14, -0.31. Example 18: Preparation of ((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((1S,4R)-5,8-dimethyl-3-(trimethylgermanyl)-1,2,3,4,4a,8b-hexahydro-1,4-methylenebisbenzocyclopenten-2-yl)-3,4-dihydro-2H-pyran-6-yl)trimethylgermanane

[0031] 0.2 mmol of cesium carbonate, 0.2 mmol of (1R,4S)-5,8-dimethyl-1,4,4a,8b-tetrahydro-1,4-methylenebiphenyl, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylgermanane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 60 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na₂SO₄, filtered, concentrated, and purified by thin-layer chromatography to obtain 43.3 mg of the target product, with a yield of 51%. The NMR characterization of the compound is as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.40 – 7.29 (m,10H), 7.24 – 7.21 (m, 3H), 7.10 (dd,J= 6.5, 3.1 Hz, 2H), 6.94 (s, 2H), 4.74(d,J= 12.4 Hz, 1H), 4.58 (d,J= 12.4 Hz, 1H), 4.55 – 4.43 (m, 3H), 4.40 – 1.35(m, 2H), 3.97 (d,J= 2.4 Hz, 1H), 3.88 (t,J= 2.7 Hz, 1H), 3.80 (dd,J= 10.5,7.2 Hz, 1H), 3.51 (dd,J= 10.5, 4.7 Hz, 1H), 3.21 (s, 2H), 2.77 (d,J= 10.4 Hz,1H), 2.30 (s, 1H), 2.20 (s, 3H), 2.19 (s, 4H), 1.34 (d,J= 9.8 Hz, 1H), 1.25(dd,J= 10.5, 2.1 Hz, 1H), 0.89 (d,J= 9.8 Hz, 1H), 0.46 (s, 9H), 0.07 (s, 9H); 13C NMR (101 MHz, Chloroform-d) δ 159.94, 144.69, 143.81, 138.39, 138.26,138.21, 129.24, 128.86, 128.36, 128.29, 128.26, 128.06, 127.74, 127.66,127.52, 127.49, 127.43, 127.27, 117.98, 74.43, 73.09, 72.20, 71.12, 71.00,70.62, 69.70, 51.76, 50.01, 47.60, 41.24, 40.00, 39.24, 30.99, 16.44, 16.25, -0.03, -0.05. Example 19: Preparation of ((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((Z)-2-(trimethylsilyl)vinyl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0032] 0.2 mmol of cesium carbonate, 0.2 mmol of dimethyl(1R,4S)-7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid ester, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 80 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na2SO4, filtered, concentrated, and purified by thin-layer chromatography to obtain 50.9 mg of the target product, with a yield of 87%. The NMR characterization of the compound is as follows: 1H NMR (400 MHz, Chloroform-d) δ 7.42 –7.28 (m, 15H), 6.99 (dd,J= 15.0, 1.3 Hz, 1H), 5.83 (d,J= 14.9 Hz, 1H), 4.84(d,J= 11.3 Hz, 1H), 4.75 (d,J= 11.3 Hz, 1H), 4.71 – 4.61 (m, 4H), 4.30 (d,J=5.8 Hz, 1H), 4.07 – 3.94 (m, 2H), 3.92 – 3.81 (m, 2H), 0.21 (s, 9H), 0.18 (s,9H); 13 C NMR (101 MHz, Chloroform-d) δ 156.04, 142.82, 138.50, 138.47, 138.26,135.40, 128.35, 128.26, 128.23, 127.97, 127.79, 127.66, 127.49, 127.38,122.88, 81.12, 76.52, 74.94, 73.53, 73.37, 72.51, 68.79, 0.32, -0.73. Example 20: Preparation of ((2R,3R,4R)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((Z)-2-(trimethylsilyl)vinyl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0033] 0.2 mmol of cesium carbonate, 0.2 mmol of dimethyl(1R,4S)-7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid ester, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2S,3R,4R)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilylane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 80 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na2SO4, filtered, concentrated, and purified by thin-layer chromatography to obtain 36.4 mg of the target product, with a yield of 62%. The NMR characterization of the compound is as follows: 1H NMR (400 MHz, Chloroform-d) δ 7.37 –7.27 (m, 15H), 7.01 (dd,J= 14.9, 0.8 Hz, 1H), 5.70 (d,J= 14.9 Hz, 1H), 4.75(dd,J= 11.9, 5.0 Hz, 2H), 4.68 (d,J= 12.2 Hz, 1H), 4.60 – 4.55 (m, 2H), 4.46 (s, 1H), 4.35 – 4.31 (m, 1H), 4.01 (d,J= 3.9 Hz, 1H), 3.97 (d,J= 4.0 Hz, 1H),3.87 (dd,J= 5.6, 2.8 Hz, 2H), 0.14 (s, 9H), 0.03 (s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 154.59, 144.54, 138.88, 138.43, 134.31, 128.30, 128.10,127.78, 127.59, 127.54, 127.53, 127.48, 127.30, 122.29, 75.19, 74.28, 73.81,73.51, 73.36, 72.02, 68.63, 0.05, -0.87. Example 21: Preparation of ((2S,3R,4S)-5-((Z)-2-(dimethyl-1,3-silyl)vinyl)-3,4-dimethoxy-2-(methoxymethyl)-3,4-dihydro-2H-pyran-6-yl)trimethylsilane

[0034] 0.2 mmol of cesium carbonate, 0.2 mmol of dimethyl(1R,4S)-7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid ester, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-5-iodo-3,4-diethoxy-2-(ethoxymethyl)-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylsilane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 80 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na2SO4, filtered, concentrated, and purified by thin-layer chromatography to obtain 17.7 mg of the target product, with a yield of 49%. The NMR characterization of the compound is as follows: 1H NMR (400 MHz, Chloroform-d) δ 6.83 (dd,J= 15.0,1.2 Hz, 1H), 5.72 (d,J= 15.1 Hz, 1H), 3.91 (d,J= 6.0 Hz, 1H), 3.82 – 3.78 (m,1H), 3.63 (dd,J= 6.1, 3.9 Hz, 2H), 3.54 – 3.49 (m, 4H), 3.40 (s, 3H), 3.36(s, 3H), 0.11 (s, 18H); 13 C NMR (101 MHz, Chloroform-d) δ 156.99, 142.31,134.77, 122.77, 81.25, 76.19, 75.70, 71.04, 59.45, 58.96, 56.77, 0.27, -0.90. Example 22: Preparation of ((2S,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-((Z)-2-(trimethylgermanyl)vinyl)-3,4-dihydro-2H-pyran-6-yl)trimethylgermanane

[0035] 0.2 mmol of cesium carbonate, 0.2 mmol of dimethyl(1R,4S)-7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid ester, 0.01 mmol of palladium acetate, 0.02 mmol of tris(2-furanyl)phosphine, 0.1 mmol of (2R,3R,4S)-3,4-di(benzyloxy)-2-((benzyloxy)methyl)-5-iodo-3,4-dihydro-2H-pyran, 0.2 mmol of hexamethylgermanane, and 1 mL of acetonitrile were added to a 15 mL reaction tube and placed in an oil bath at 80 °C for 24 h. After cooling to room temperature, the reaction solution was diluted with ethyl acetate, washed three times with water, dried over anhydrous Na2SO4, filtered, concentrated, and purified by thin-layer chromatography to obtain 38.6 mg of the target product, with a yield of 57%. The NMR characterization of the compound is as follows: 1H NMR (400 MHz, Chloroform-d) δ 7.36 –7.25 (m, 15H), 6.92 (dd,J= 13.8, 1.2 Hz, 1H), 5.92 (d,J= 13.8 Hz, 1H), 4.80 (d,J= 11.3 Hz, 1H), 4.69 (d,J= 11.3 Hz, 1H), 4.62 (d,J= 2.4 Hz, 2H), 4.57 (s,2H), 4.30 (d,J= 5.8 Hz, 1H), 4.01 – 3.93 (m, 2H), 3.87 – 3.77 (m, 2H), 0.30(s, 9H), 0.27(s, 9H); 13 C NMR (101 MHz, Chloroform-d) δ 159.08, 140.78,138.59, 138.47, 138.27, 136.19, 128.36, 128.30, 128.23, 128.01, 127.74,127.68, 127.45, 127.43, 120.78, 80.36, 76.85, 74.49, 73.44, 73.39, 71.70,68.76, 0.04, -0.92. Those skilled in the art should understand that the above embodiments are merely illustrative and are not intended to imply that the scope of the invention is limited to these examples. Within the framework of this invention, technical features of the above embodiments or different embodiments can be combined, steps can be implemented in any order, and many other variations of the different aspects of the invention as described above exist, which are not provided in detail for the sake of brevity. Any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A method for preparing a silicon / germanium-glycoside compound, characterized in that, Includes the following steps: (1) Add base, olefin, palladium catalyst, ligand, 5-halogenated enose, hexamethylsilyl (or hexamethylgerman) and organic solvent sequentially to a high-temperature dry reaction vessel, and react at 50~100℃ for 15~30h; The molar ratio of 5-haloenose, hexamethylsilyl (or hexamethylgermanane), olefin, palladium catalyst, ligand and base is 0.8~1.2:1.0~3.0:1.0~3.0:0.08~0.12:0.18~0.22:1.0~3.0, and the organic solvent corresponding to each mole of 5-iodoenose is 1~3L; (2) The material obtained in step (1) is diluted with ethyl acetate and then washed with water to separate the organic phase; (3) The organic phase obtained in step (2) is dried, filtered, concentrated, and subjected to thin-layer chromatography or column chromatography to obtain the Si / Ge-glycoside derivative; The structural formula of the 5-halogenated enose is: Where X is a halogen and P is hydrogen, alkyl, alkoxy, acyl, aryl, or benzyl; The structural formula of the olefin is as follows: Where Y is C, O, or N, R1 is hydrogen, alkyl, acyl, aryl, carboxylic acid, ester, amide, sulfonyl, or trifluoromethyl, and R2 is hydrogen, alkyl, aryl, acyl, carboxylic acid, ester, amide, sulfonyl, or trifluoromethyl.

2. The preparation method according to claim 1, characterized in that: The palladium catalyst is palladium acetate, palladium trifluoroacetate, palladium dichloride, bis(triphenylphosphine)dichloride, bis(acetonitrile)dichloride, palladium acetylacetonate, palladium diacetylacetonate, palladium diacetylacetonate, allyl palladium chloride dimer, tetra(triphenylphosphine)palladium, [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride or tris(dibenzylacetone)dipalladium. The ligands are triphenylphosphine, tris(2-furanyl)phosphine, 2-dicyclohexylphosphine-2',6'-diisopropoxy-1,1'-biphenyl, trinaphthylphosphine, 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl, 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl, tricyclohexylphosphine, 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, pyridine, bipyridine, 2-hydroxy-3-trifluoromethylpyridine, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 1,1'-bis(diphenylphosphine)ferrocene, or 1,1'-bi-2-naphthol; The base is sodium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, sodium carbonate, sodium phosphate, potassium carbonate, potassium phosphate, potassium dihydrogen phosphate, cesium carbonate, cesium acetate, cesium hydroxide, or 1,8-diazabicycloundec-7-ene. The organic solvent is dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexafluoroisopropanol, 1,2-dichloroethane, toluene, 1,4-dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether, polyethylene glycol dimethyl ether, or ethylene glycol diethyl ether.

3. The preparation method according to claim 2, characterized in that: The halogen is fluorine, iodine, chlorine, or bromine.

4. The preparation method according to claim 2, characterized in that: The palladium catalyst is palladium acetate, the ligand is tris(2-furanyl)phosphine, the base is cesium carbonate, and the organic solvent is acetonitrile or N-methylpyrrolidone.

5. The preparation method according to claim 1, characterized in that: The reaction temperature in step (1) is 60~80℃.

6. The preparation method according to claim 1, characterized in that: The reaction time in step (1) is 24 hours.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The molar ratio of the 5-haloenose, hexamethylsilyl (or hexamethylgermanane), olefin, palladium catalyst, ligand and base is 1:2:2:0.1:0.2:2, and the organic solvent corresponding to each mole of 5-haloenose is 1~2L.

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