A method for the synthesis of a functionalized carbon glycoside

Abstract

The application discloses a synthesis method of a functionalized carbon glycoside, and belongs to the technical field of organic synthesis. The application takes a coupling reagent (aryl bromide, alkenyl bromide, alkenyl geminal difluoride, alkynyl bromide, electron-deficient olefin) and a glycoside as substrates, is catalyzed by a photocatalyst, or is cooperatively catalyzed by a photocatalyst and a metal catalyst, and is completely reacted under the irradiation of purple light to obtain a functionalized (arylated, alkenylated, alkenyl monofluorinated, alkynylated and alkylated) carbon glycoside. The application realizes the stereoselective functionalization reaction of a C(sp 3 )‑H bond of the glycoside by using the strategy of photocatalysis or light-metal cooperative catalysis, the method has the advantages of mild conditions, wide substrate adaptability, low cost, high atom utilization rate and economic steps, and the synthesized functionalized carbon glycoside can realize the synthesis of various natural products and commercially available drugs through subsequent conversion, and has great synthetic value.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and specifically to a method for synthesizing functionalized carbon glycosides. Background Technology

[0002] Carbon glycosides exhibit higher stability and better drug-like properties compared to oxyglycosides, making carbon glycosylation an effective strategy for modifying glycoconjugated drugs. The efficient synthesis of carbon glycosides is receiving increasing attention in fields such as glycochemistry and pharmaceutical research and development. It represents a cutting-edge area of ​​chemistry and its interdisciplinary sciences, and is a major national strategic need in the life and health sector.

[0003] Due to the diversity and structural complexity of sugars, a unified synthetic method is lacking, and the efficient synthesis of carboxyglycosides has always been a challenge in the field of glycochemistry. Traditional methods for synthesizing carboxyglycosides include Friedel-Crafts glycosylation reactions between electron-rich aromatic hydrocarbons and sugar donors, or coupling of metal reagents with glycosyl donors to construct carboxyglycosidic bonds. These methods suffer from limitations such as low efficiency, poor selectivity, and poor atom economy. Therefore, developing efficient and highly stereoselective methods for synthesizing carboxyglycosides is of great significance for both glycochemistry and pharmaceutical research and development. Summary of the Invention

[0004] To address the shortcomings of the existing technologies, this invention provides a method for synthesizing functionalized carbon glycosides. By utilizing photocatalysis or photo-metal synergistic catalysis to selectively activate the CH bond of the glycoside, functionalized carbon glycosides can be synthesized efficiently. The synthesized carbon glycosides can be used to synthesize various commercially available drugs through subsequent transformations, demonstrating significant synthetic value.

[0005] To achieve the above objectives, the specific technical solution of the present invention is as follows:

[0006] A method for synthesizing a functionalized carbon glycoside involves mixing materials including coupling reagent A, glycoside B, and a photocatalyst with a solvent under an inert atmosphere, and reacting completely under ultraviolet light to obtain a functionalized carbon glycoside C; wherein the coupling reagent A is one of aryl bromides, alkenyl bromides, alkenyl gemini difluorides, alkynyl bromides, and electron-deficient alkenes.

[0007] Preferably, the coupling reagent A is selected from one of the following structures:

[0008]

[0009] Preferably, glycoside B is selected from one of 1-deoxyglycosides, glucose or mannose derivatives, 2-deoxyglycosides, unprotected glycosides, and glycosides protected by a protecting group; wherein, the 1-deoxyglycoside is selected from one of the following structures:

[0010]

[0011] The glucose or mannose derivative is selected from one of the following structures:

[0012]

[0013] The 2-deoxyglycoside is selected from one of the following structures:

[0014]

[0015] The unprotected glycoside is selected from one of the following structures:

[0016]

[0017] The glycoside protected by the protecting group is selected from one of the following structures:

[0018]

[0019] Preferably, the photocatalyst is selected from one of the following structures:

[0020]

[0021] Preferably, the material further includes one or more of a metal catalyst, a ligand, and a base. Different reaction conditions can be selected according to different coupling reagents. For example, when the coupling reagent is an aryl bromide, the synergistic effect of a photocatalyst and a metal catalyst, as well as the combination of a suitable ligand and a base, is required for the complete reaction with the glycoside. When the coupling reagent is an alkenyl bromide or an alkenyl gemini difluoride, the synergistic effect of a photocatalyst and a metal catalyst, as well as the combination of a suitable base, is required for the complete reaction with the glycoside. When the coupling reagent is an alkynyl bromide, the combination of a photocatalyst and a suitable base is required for the complete reaction with the glycoside. When the coupling reagent is an electron-deficient olefin, only the addition of a photocatalyst is needed for the complete reaction with the glycoside.

[0022] Preferably, the metal catalyst is a nickel catalyst or an iron catalyst, and the catalyst includes, but is not limited to, one of nickel chloride, nickel bromide, nickel chloride ethylene glycol dimethyl ether, nickel bromide ethylene glycol dimethyl ether, cyclooctadiene nickel, nickel acetylacetone, nickel perchlorate, nickel iodide, nickel acetate tetrahydrate, and ferric dibromide.

[0023] More preferably, the metal catalyst is nickel bromide ethylene glycol dimethyl ether or ferric dibromide.

[0024] Preferably, the ligand is selected from one of the following structures:

[0025]

[0026] More preferably, the ligand is 4,4′-di-tert-butyl-2,2′-bipyridine (i.e., the structure shown in D) or 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-tert-bipyridine (i.e., the structure shown in F).

[0027] Preferably, the alkali includes, but is not limited to, one of sodium carbonate, potassium carbonate, potassium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, sodium bicarbonate, lithium carbonate, cesium carbonate, sodium phosphate, and sodium acetate.

[0028] More preferably, the alkali is potassium phosphate.

[0029] Preferably, the solvent includes, but is not limited to, a mixture of one or more of acetonitrile, acetone, water, and dimethyl sulfoxide.

[0030] Preferably, the reaction temperature is 25 °C and the reaction time is 48~60 h.

[0031] Preferably, the molar ratio of the coupling reagent, glycoside, metal catalyst, ligand, photocatalyst, and base is 1: 5: 0.1: 0.15: 0.02: 1.2, wherein the concentration of the coupling reagent is 0.1~0.2 mol / L.

[0032] Preferably, the violet light is 390 nm violet light.

[0033] This invention utilizes coupling reagents (aryl bromides, alkenyl bromides, alkenyl gemini difluorides, alkynyl bromides, and electron-deficient alkenes) and glycosides as substrates to yield functionalized C-glycosides. First, the C-H bonds of the glycoside are directly broken using a visible light-promoted hydrogen atom transfer (HAT) process to generate glycoside radicals. These radicals are then coupled with coupling reagents (aryl bromides, alkenyl bromides, alkenyl gemini difluorides, alkynyl bromides, and electron-deficient alkenes), or, under the synergistic catalysis of a metal catalyst, the glycoside radicals are coupled with coupling reagents (aryl bromides, alkenyl bromides, alkenyl gemini difluorides, alkynyl bromides, and electron-deficient alkenes) to achieve the coupling of glycoside C(sp...)... 3 Stereoselective functionalization of the C-H bond yields functionalized carbon glycosides. This invention utilizes a simple photocatalytic or photo-metal co-catalytic strategy to achieve stereoselective functionalization of the C-H bond in glycosides, such as arylation, alkenylation, alkenyl monofluorination, alkynylation, and alkylation. The synthesized carbon glycosides, through subsequent transformations, can be used to synthesize various commercially available drugs, demonstrating significant synthetic value.

[0034] Compared with the prior art, the advantages of the present invention are:

[0035] 1. This invention provides a strategy of photocatalytic hydrogen atom transfer and metal co-catalysis to directly break the carbon-hydrogen bonds of glycosides to achieve enantioselective functionalization (arylation, alkenylation, alkenyl monofluorination, alkyneation and alkylation), and to prepare a series of carbon glycoside compounds.

[0036] 2. The method of this invention has mild reaction conditions, good functional group tolerance, and a wide range of applicable substrates. It is an efficient, green, and inexpensive method for synthesizing carbon glycosides. In addition, this invention directly uses simple and stable glycosides as raw materials, avoiding the use of precious metal catalysts and equivalent redox reagents, which greatly reduces the synthesis cost. Detailed Implementation

[0037] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0038] This invention provides a method for synthesizing a functionalized carbon glycoside. The method involves mixing materials including coupling reagent A, glycoside B, and a photocatalyst with a solvent under an inert atmosphere, and reacting completely under ultraviolet light irradiation to obtain a functionalized carbon glycoside C. The coupling reagent A is one of aryl bromides, alkenyl bromides, alkenyl gemini difluorides, alkynyl bromides, and electron-deficient alkenes.

[0039] In some examples, the coupling agent is selected from one of the following structures:

[0040]

[0041] In some examples, glycoside B is selected from one of 1-deoxyglycosides, glucose or mannose derivatives, 2-deoxyglycosides, unprotected glycosides, and glycosides protected by a protecting group; wherein, the 1-deoxyglycoside is selected from one of the following structures:

[0042]

[0043] The glucose or mannose derivative is selected from one of the following structures:

[0044]

[0045] The 2-deoxyglycoside is selected from one of the following structures:

[0046]

[0047] The unprotected glycoside is selected from one of the following structures:

[0048]

[0049] The glycoside protected by the protecting group is selected from one of the following structures:

[0050]

[0051] In some examples, the photocatalyst is selected from one of the following structures:

[0052]

[0053] In some examples, the material also includes one or more of a metal catalyst, a ligand, and a base.

[0054] In some examples, the metal catalyst is a nickel catalyst or an iron catalyst, and the catalyst includes, but is not limited to, one of nickel chloride, nickel bromide, nickel chloride ethylene glycol dimethyl ether, nickel bromide ethylene glycol dimethyl ether, cyclooctadiene nickel, nickel acetylacetone, nickel perchlorate, nickel iodide, nickel acetate tetrahydrate, and ferric dibromide.

[0055] In some examples, the ligand is selected from one of the following structures:

[0056]

[0057] In some examples, the alkali includes, but is not limited to, one of sodium carbonate, potassium carbonate, potassium phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, sodium bicarbonate, lithium carbonate, cesium carbonate, sodium phosphate, and sodium acetate.

[0058] In some examples, the reaction temperature is 25 °C and the reaction time is 48–60 h.

[0059] In some examples, the solvent includes, but is not limited to, a mixture of one or more of acetonitrile, acetone, water, and dimethyl sulfoxide.

[0060] In the following specific embodiments, D is 4,4'-di-tert-butyl-2,2'-bipyridine, E is tetrabutylammonium decatungstate, F is 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-tert-bipyridine, and G is (4-methoxyphenyl)(4-(trifluoromethyl)phenyl) ketone. All materials and solvents used are commercially available.

[0061] Example 1

[0062]

[0063] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). Product 1 (38.5 mg, 66% yield, β / α > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 7.97 – 7.92 (m,2H), 7.52 – 7.46 (m, 2H), 5.06 (t, J = 5.7 Hz, 1H), 4.99 (d, J = 5.9 Hz, 1H,anomeric H), 4.95 (t, J = 5.5 Hz, 1H), 4.24 (p, J = 6.2 Hz, 1H), 2.59 (s,3H), 2.10 (s, 3H), 2.09 (s, 3H), 1.46 (d, J = 6.4 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.7, 169.9, 169.8, 144.0, 137.0, 128.6, 126.1, 81.9, 78.0, 76.7,75.4, 26.7, 20.69, 20.65, 19.0. HRMS: (ESI) calcd for C 17 H 21 O6 + [M+H] + 321.1333, found 321.1327.

[0064] Example 2

[0065]

[0066] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 4-bromobenzonitrile (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). Product 2 (43.6 mg, 72% yield, β / α > 20 / 1) was obtained by column chromatography.1 H NMR (600 MHz, CDCl3) δ 7.67 – 7.63 (m,2H), 7.52 (d, J = 8.1 Hz, 2H), 5.03 (t, J = 5.6 Hz, 1H), 4.97 (d, J = 5.8 Hz,1H, anomeric H), 4.90 (t, J = 5.6 Hz, 1H), 4.24 (p, J = 6.2 Hz, 1H), 2.10 (s,3H), 2.09 (s, 3H), 1.45 (d, J = 6.4 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 169.9,169.8, 144.2, 132.4, 126.6, 118.7, 112.0, 81.7, 78.0, 76.7, 75.3, 20.7, 20.6,18.9. HRMS: (ESI) calcd for C 16 H 18 NO5 + [M+H] + 304.1179, found 304.1176.

[0067] Example 3

[0068]

[0069] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), ethyl 4-bromobenzoate (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 3 (44.8 mg, 64% yield, β / α > 20 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 8.06 –8.01 (m, 2H), 7.49 – 7.44 (m, 2H), 5.06 (t, J = 5.8 Hz, 1H), 4.99 (d, J = 6.0Hz, 1H, anomeric H), 4.96 (t, J = 5.5 Hz, 1H), 4.37 (q, J = 7.1 Hz, 2H), 4.23 (p, J = 6.2 Hz, 1H), 2.10 (s, 3H), 2.08 (s, 3H), 1.46 (d, J = 6.4 Hz, 3H), 1.38 (t, J = 7.1 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 169.9, 169.8, 166.3,143.7, 130.4, 129.8, 125.9, 81.9, 78.0, 76.8, 75.4, 61.0, 20.7, 20.6, 19.0,14.3. HRMS: (ESI) calcd for C 18 H 23 O7 + [M+H] + 351.1438, found 351.1439.

[0070] Example 4

[0071]

[0072] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 4-bromobenzyl sulfone (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 4 (44.9 mg, 63% yield, β / α > 20 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 7.94 – 7.90 (m,2H), 7.63 – 7.58 (m, 2H), 5.04 (t, J = 5.5 Hz, 1H), 5.01 (d, J = 5.8 Hz, 1H,anomeric H), 4.90 (t, J = 5.5 Hz, 1H), 4.25 (p, J = 6.2 Hz, 1H), 3.04 (s,3H), 2.10 (s, 3H), 2.09 (s, 3H), 1.46 (d, J = 6.4 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 169.9, 169.8, 145.2, 140.3, 127.7, 126.8, 81.6, 78.0, 76.7, 75.3,44.6, 20.7, 18.9. HRMS: (ESI) calcd for C 16 H 21 O7S + [M+H] + 357.1002, found 357.1004.

[0073] Example 5

[0074]

[0075] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 4'-bromoacetanilide (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 5 (35.5 mg, 53% yield, β / α > 20 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 7.55 –7.45 (m, 3H), 7.32 (d, J = 8.3 Hz, 2H), 5.04 (t, J = 5.9 Hz, 1H), 4.97 (t, J= 5.4 Hz, 1H), 4.90 (d, J = 6.2 Hz, 1H, anomeric H), 4.19 (p, J = 6.2 Hz,1H), 2.15 (s, 3H), 2.09 (s, 3H), 2.06 (s, 3H), 1.44 (d, J = 6.5 Hz, 3H). 13 CNMR (151 MHz, CDCl3) δ 169.9, 169.8, 168.4, 137.9, 134.2, 126.8, 119.9, 81.9,77.8, 76.7, 75.4, 24.5, 20.7, 20.6, 19.0. HRMS: (ESI) calcd for C 17 H 22 NO6 + [M+H] + 336.1442, found 336.1439.

[0076] Example 6

[0077]

[0078] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), methyl 5-bromo-2-furfurylate (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 6 (37.8 mg, 58% yield, β / α > 20 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 7.13 (d, J= 3.5 Hz, 1H), 6.48 (d, J = 3.5 Hz, 1H), 5.45 (t, J = 5.6 Hz), 5.04 (t, J =5.7 Hz, 1H), 4.97 (d, J = 5.6 Hz, 1H, anomeric H), 4.16 (p, J = 6.3 Hz, 1H), 3.87 (s, 3H), 2.09 (s, 3H), 2.07 (s, 3H), 1.40 (d, J = 6.4 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 169.8, 169.6, 158.9, 155.3, 144.8, 118.6, 110.3, 77.9,76.2, 75.4, 73.8, 52.0, 20.63, 20.56, 18.9. HRMS: (ESI) calcd for C 15 H 19 O8 + [M+H] + 327.1074, found 327.1071.

[0079] Example 7

[0080]

[0081] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 5-bromo-2-trifluoromethylpyridine (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 7 (41.6 mg, 60% yield, β / α > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 8.77 –8.73 (m, 1H), 7.94 (dd, J = 8.3, 2.1 Hz, 1H), 7.69 (d, J = 8.1 Hz, 1H), 5.06– 5.00 (m, 2H), 4.95 (t, J = 5.0 Hz, 1H), 4.27 (p, J = 6.2 Hz, 1H), 2.12 (s,3H), 2.10 (s, 3H), 1.46 (d, J = 6.4 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 169.9,169.7, 148.1 (q, J = 34.8 Hz), 148.0, 137.7, 134.9, 121.5 (q, J = 274.0 Hz), 120.4 (q, J = 2.8 Hz), 79.6, 78.6, 76.4, 75.3, 20.7, 20.6, 19.0. 19 F NMR (565MHz, CDCl3) δ -67.90. HRMS: (ESI) calcd for C 15 H 17 NO5F3 + [M+H] + 348.1053, found348.1041.

[0082] Example 8

[0083]

[0084] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 5-bromopyrimidine (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 8 (37.5 mg, 67% yield, β / α > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 9.18 (s, 1H),8.77 (s, 2H), 5.04 (t, J = 6.0 Hz, 1H), 4.98 – 4.93 (m, 2H), 4.25 (p, J = 6.2Hz, 1H), 2.11 (s, 3H), 2.09 (s, 3H), 1.46 (d, J = 6.4 Hz, 3H). 13 C NMR (151MHz, CDCl3) δ 169.8, 169.7, 158.7, 154.9, 132.2, 78.6, 78.4, 76.2, 75.3,20.7, 20.6, 19.0. HRMS: (ESI) calcd for C 13 H 17 N2O5 + [M+H] + 281.1132, found 281.1128.

[0085] Example 9

[0086]

[0087] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S2 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). Product 9 (49.1 mg, 65% yield, β / α > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 8.0 – 7.9 (m,2H), 7.5 – 7.5 (m, 2H), 5.26 (t, J = 4.9 Hz, 1H), 5.09 – 5.07 (m, 1H), 5.06(d, J = 6.4 Hz, 1H, anomeric H), 4.48 (dd, J = 12.0, 3.0 Hz, 1H), 4.41 – 4.36 (m, 1H), 4.32 (dd, J = 12.1, 4.2 Hz, 1H), 2.61 (s, 3H), 2.19 – 2.02 (m, 9H). 13C NMR (151 MHz, CDCl3) δ 197.7, 170.6, 169.8, 169.7, 143.5, 137.1, 128.7,126.0, 81.7, 80.0, 76.6, 71.4, 63.4, 26.7, 20.9, 20.7, 20.6. HRMS: (ESI)calcd for C 19 H 23 O8 + [M+H] + 379.1387, found 379.1386.

[0088] Example 10

[0089]

[0090] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), methyl p-bromobenzoate (0.2 mmol), glycoside S3 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 10 (63.3 mg, 58% yield, β / α > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 8.04 –7.98 (m, 2H), 7.74 – 7.67 (m, 4H), 7.54 – 7.50 (m, 2H), 7.47 – 7.41 (m, 2H),7.42 – 7.35 (m, 4H), 4.94 (d, J = 5.5 Hz, 1H, anomeric H), 4.81 (dd, J = 6.6,3.6 Hz, 1H), 4.51 (dd, J = 6.6, 5.5 Hz, 1H), 4.24 (q, J = 3.6 Hz, 1H), 3.97(dd, J = 11.3, 3.3 Hz, 1H), 3.92 (s, 3H), 3.89 (dd, J = 11.3, 3.8 Hz, 1H), 1.64 (s, 3H), 1.37 (s, 3H), 1.06 (s, 9H). 13C NMR (151 MHz, CDCl3) δ 167.0,145.3, 135.7, 133.2, 133.1, 129.9, 129.8, 129.7, 129.5, 127.80, 127.77,125.6, 114.7, 86.9, 85.4, 84.5, 81.7, 64.0, 52.1, 27.7, 26.8, 25.6, 19.3.

[0091] Example 11

[0092]

[0093] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S5 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic dome. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 11 (51.8 mg, 56% yield, α / β > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 8.12 (dd, J =8.4, 1.4 Hz, 2H), 7.99 (d, J = 8.4 Hz, 2H), 7.65 (dd, J = 8.3, 1.4 Hz, 2H),7.60 – 7.54 (m, 3H), 7.53 (tt, J = 7.4, 1.3 Hz, 1H), 7.46 (t, J = 7.8 Hz,2H), 7.33 (dd, J = 8.3, 7.4 Hz, 2H), 5.70 (dt, J = 16.1, 2.0 Hz, 1H), 5.57(dd, J = 20.9, 2.8 Hz, 1H, anomeric H), 5.30 (ddd, J = 51.0, 2.8, 1.7 Hz,1H), 4.78 – 4.73 (m, 2H), 4.67 (q, J = 7.6 Hz, 1H), 2.61 (s, 3H). 13C NMR (151MHz, CDCl3) δ 197.5, 165.7 (d, J = 172.9 Hz), 143.0 (d, J = 8.1 Hz), 136.8,133.4 (d, J = 74.1 Hz), 129.8, 129.62, 129.61, 128.7, 128.5, 128.4 (d, J =3.7 Hz), 125.7, 100.9, 99.6, 84.1 (d, J = 25.8 Hz), 82.3 (d, J = 1.9 Hz), 78.5 (d, J = 29.4 Hz), 64.0 (d, J = 2.5 Hz), 26.6. 19 F NMR (565 MHz, CDCl3) δ-182.7 (ddd, J = 51.2, 21.0, 16.1 Hz). HRMS: (ESI) calcd for C 27 H 24 FO6 + [M+H] + 463.1551, found 463.1553.

[0094] Example 12

[0095]

[0096] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S6 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 12 (52.9 mg, 63% yield, dr > 20 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 7.95 – 7.92(m, 2H), 7.60 (d, J = 8.2 Hz, 2H), 5.84 (d, J = 3.7 Hz, 1H), 5.30 (d, J = 3.1Hz, 1H), 5.13 (d, J = 7.0 Hz, 1H), 4.47 (d, J = 3.7 Hz, 1H), 4.35 (dd, J =8.7, 3.1 Hz, 1H), 4.03 (dd, J = 8.7, 7.1 Hz, 1H), 2.59 (s, 3H), 2.00 (s, 3H), 1.56 (s, 3H), 1.49 (s, 6H), 1.31 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.8,169.6, 144.5, 136.6, 128.3, 127.0, 112.2, 110.3, 105.1, 83.1, 82.0, 80.6,78.9, 76.3, 27.0, 26.9, 26.7, 26.6, 26.1, 20.7. HRMS: (ESI) calcd forC 22 H 28 O8Na + [M+Na] + 443.1676, found 443.1666.

[0097] Example 13

[0098]

[0099] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S7 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic dome. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 13 (61.3 mg, 73% yield, dr > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 7.95 – 7.90(m, 2H), 7.58 – 7.53 (m, 2H), 5.10 (d, J = 8.1 Hz, 1H), 4.16 (dd, J = 6.0,4.6 Hz, 1H), 4.13 – 4.08 (m, 2H), 4.03 (dd, J = 8.1, 4.6 Hz, 1H), 3.98 – 3.94(m, 1H), 3.93 – 3.88 (m, 1H), 2.58 (s, 3H), 1.55 (s, 3H), 1.50 (s, 3H), 1.35(s, 3H), 1.34 (s, 3H), 1.31 (s, 3H), 1.24 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ197.7, 144.0, 136.9, 128.5, 127.3, 110.2, 109.9, 109.8, 83.1, 79.5, 79.4,78.5, 76.8, 67.1, 27.5, 27.2, 27.1, 27.0, 26.7, 26.4, 25.4. HRMS: (ESI) calcdfor C 23 H 32 O7Na + [M+Na] + 443.2040, found 443.2026.

[0100] Example 14

[0101]

[0102] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S8 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic dome. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 14 (61.2 mg, 78% yield, dr > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 7.90 – 7.85(m, 2H), 7.55 – 7.48 (m, 2H), 5.03 (d, J = 6.5 Hz, 1H), 4.32 – 4.26 (m, 1H), 3.85 – 3.78 (m, 2H), 3.65 (s, 3H), 2.78 (dd, J = 15.7, 3.7 Hz, 1H), 2.59 –2.53 (m, 4H), 1.44 (s, 3H), 1.43 (s, 3H), 1.33 (s, 3H), 1.14 (s, 3H). 13 C NMR(151 MHz, CDCl3) δ 197.9, 171.0, 144.6, 136.6, 128.3, 126.9, 110.4, 110.0,83.6, 81.8, 81.2, 51.8, 38.4, 27.2, 27.00, 26.98, 26.8, 26.7. HRMS: (ESI)calcd for C 21 H 28 O7Na + [M+Na] + 415.1727, found 415.1718.

[0103] Example 15

[0104]

[0105] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S9 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 15 (50.7 mg, 67% yield, β / α > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 7.93 – 7.91 (m,2H), 7.45 – 7.41 (m, 2H), 5.33 (t, J = 9.5 Hz, 1H), 5.15 (td, J = 10.1, 5.7Hz, 1H), 5.04 (t, J = 9.6 Hz, 1H), 4.36 (d, J = 9.8 Hz, 1H, anomeric H), 4.28 (dd, J = 11.3, 5.7 Hz, 1H), 3.46 (t, J = 11.0 Hz, 1H, H 5b ), 2.59 (s, 3H), 2.06 (s, 3H), 2.02 (s, 3H), 1.81 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.6, 170.3,169.9, 168.9, 141.7, 137.3, 128.4, 127.2, 80.3, 73.5, 72.7, 69.2, 67.2, 26.6,20.7, 20.4. HRMS: (ESI) calcd for C 19 H 23 O8 + [M+H] + 379.1387, found 379.1380.

[0106] Example 16

[0107]

[0108] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S10 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 16 (55.8 mg, 62% yield, α / β > 20 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 8.01 (d, J =8.4 Hz, 2H), 7.60 (d, J = 8.2 Hz, 2H), 5.93 (t, J = 3.4 Hz, 1H), 5.31 (t, J =8.4 Hz, 1H), 5.16 – 5.10 (m, 2H), 4.42 (dd, J = 12.1, 6.5 Hz, 1H), 4.14 (dd,J = 12.1, 2.9 Hz, 1H), 3.77 (ddd, J = 8.1, 6.5, 2.9 Hz, 1H), 2.61 (s, 3H), 2.14 (s, 3H), 2.12 (s, 3H), 2.07 (s, 3H), 2.02 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.4, 170.6, 170.2, 170.1, 169.6, 140.6, 137.1, 129.0, 126.8, 75.0,71.8, 69.3, 69.0, 66.8, 62.2, 26.7, 20.9, 20.74, 20.70, 20.69. HRMS: (ESI)calcd for C 22 H 27 O 10 + [M+H] + 451.1599, found 451.1607.

[0109] Example 17

[0110]

[0111] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S13 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 17 (49.8 mg, 78% yield, α / β = 1.5 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 7.95 – 7.89(m, 2H), 7.45 – 7.39 (m, 2H), 5.25 – 5.13 (m, 2H), 4.44 – 4.36 (m, 1H), 4.27– 4.21 (m, 2H), 2.85 – 2.79 (m, 1H), 2.61 – 2.55 (m, 3H), 2.13 – 2.08 (m,3H), 2.08 – 1.93 (m, 4H). 13 C NMR (151 MHz, CDCl3) δ 197.75, 197.70, 170.74,170.67, 170.5, 147.6, 146.2, 136.7, 136.4, 128.6, 128.5, 125.8, 125.7, 82.9,81.8, 80.1, 79.5, 76.5, 75.6, 64.3, 64.0, 41.3, 40.3, 26.7, 21.1, 20.90,20.89, 20.8. HRMS: (ESI) calcd for C 17 H 21 O6 + [M+H] + 321.1333, found 321.1335.

[0112] Example 18

[0113]

[0114] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.04 mmol), F (0.06 mmol), p-bromoacetophenone (0.2 mmol), glycoside S14 (1.0 mmol), E (0.008 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic flux. The reaction was carried out at 25 °C for 60 hours under ultraviolet light (10 W, 390 nm), concentrated, and subjected to rapid column chromatography to give a yellow liquid product 18 (47.8 mg, 55% yield, α / β = 13 / 1). 1H NMR (600 MHz, CDCl3)δ 7.95 (d, J = 8.2 Hz, 2H), 7.87 – 7.82 (m, 2H), 7.72 (dd, J = 5.7, 2.8 Hz,2H), 7.48 (d, J = 8.1 Hz, 2H), 5.11 – 5.04 (m, 1H), 5.02 (dd, J = 13.0, 2.3Hz, 1H), 4.80 – 4.74 (m, 1H), 4.23 (dd, J = 10.6, 9.1 Hz, 1H), 4.06 (dd, J =11.0, 5.4 Hz, 1H), 3.70 (t, J = 10.5 Hz, 1H), 3.32 – 3.25 (m, 1H), 2.59 (s,3H), 2.08 – 2.02 (m, 1H), 1.45 (s, 3H), 1.14 (s, 3H). 13 C NMR (151 MHz, CDCl3)δ 197.8, 147.7, 136.7, 134.2, 133.9, 128.7, 127.4, 127.2, 126.1, 123.4,123.2, 99.6, 73.1, 67.8, 65.6, 63.6, 45.0, 32.0, 28.9, 26.7, 18.8. HRMS:(ESI) calcd for C 25 H 26 NO6 + [M+H] + 436.1755, found 436.1750.

[0115] Example 19

[0116]

[0117] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S15 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 19 (57.2 mg, 73% yield, α / β = 17 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 8.04 – 7.98 (m,2H), 7.62 – 7.57 (m, 2H), 5.21 (t, J = 4.5 Hz, 1H), 5.07 – 4.99 (m, 2H), 4.40(dd, J = 12.1, 5.9 Hz, 1H), 4.11 (dd, J = 12.1, 2.9 Hz, 1H), 3.70 (ddd, J =8.1, 5.9, 2.8 Hz, 1H), 2.74 (dt, J = 13.8, 4.0 Hz, 1H), 2.62 (s, 3H), 2.19 –2.14 (m, 1H), 2.12 (s, 3H), 2.10 (s, 3H), 2.02 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.6, 170.7, 170.3, 169.7, 143.9, 136.7, 128.9, 126.7, 71.6, 71.3,69.3, 68.6, 62.1, 31.4, 26.7, 21.1, 20.8, 20.7; HRMS: (ESI) calcd for C 20 H 25 O8 + [M+H] + 393.1544, found 393.1542.

[0118] Example 20

[0119]

[0120] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.01 mmol), D (0.015 mmol), p-bromoacetophenone (0.1 mmol), glycoside S17 (1.0 mmol), E (0.002 mmol), potassium phosphate (0.12 mmol), and anhydrous acetonitrile (1.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 20 (40.8 mg, 60% yield, α / β = 15 / 1) was obtained by column chromatography. 11H NMR (600 MHz, CDCl3) δ 8.01 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 8.1 Hz, 2H), 5.48 (d, J = 4.0 Hz, 1H), 5.35 – 5.29 (m, 1H), 5.12 (t, J = 4.7 Hz, 1H, anomeric H), 5.03 (t, J = 9.9 Hz, 1H), 4.92 (dq, J = 9.0, 4.3 Hz, 1H), 4.84 (dd, J = 10.4, 4.0 Hz, 1H), 4.40 (dd, J = 11.9, 5.8 Hz, 1H), 4.30 (dd, J = 11.9, 3.2 Hz, 1H), 4.22 (dd, J = 12.4, 4.0 Hz, 1H), 4.08 (dd, J = 12.4, 2.2 Hz, 1H), 4.01 – 3.98 (m, 1H), 3.85 (t, J = 7.1 Hz, 1H), 3.78 (td, J = 7.2, 6.6, 3.3 Hz, 1H), 2.67 – 2.63 (m, 1H), 2.62 (s, 3H), 2.61 (d, J = 2.6 Hz, 1H), 2.14 (s, 3H), 2.10 (s, 3H), 2.08 (s, 3H), 2.01 (s, 3H), 1.98 – 1.95 (m, 6H). 13 13C NMR (151 MHz, CDCl3) δ 197.6, 170.63, 170.55, 170.3, 170.2, 169.9, 169.5, 144.1, 136.7, 129.0, 126.6, 95.8, 73.3, 71.7, 71.6, 71.0, 70.2, 69.5, 68.3, 68.0, 62.7, 61.5, 31.3, 26.7, 21.2, 20.8, 20.7, 20.58, 20.55, 20.5. HRMS: (ESI) calcd for C 32 H 41 O 16 + [M+H] + 681.2935, found 681.2933.

[0121] Example 21

[0122]

[0123] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 4-bromobenzyl sulfone (0.2 mmol), glycoside S19 (1.0 mmol), G (0.04 mmol), potassium phosphate (0.24 mmol), and ethyl acetate (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 21 (26.2 mg, 48% yield, α / β = 1.4 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, Methanol-d4) δ 7.95 –7.87 (m, 2H), 7.70 – 7.64 (m, 2H), 5.24 – 5.17 (m, 1H, anomeric H), 4.40 –4.30 (m, 1H), 4.05 – 3.97 (m, 1H), 3.77 – 3.63 (m, 2H), 3.10 (s, 3H), 2.77 –2.24 (m, 1H), 1.93 – 1.83 (m, 1H). 13 C NMR (151 MHz, Methanol-d4) δ 150.3,148.9, 139.6, 139.3, 127.1, 126.5, 126.2, 88.1, 86.5, 79.3, 78.7, 72.9, 72.1,62.5, 61.9, 43.7, 43.2, 43.03 43.02. HRMS: (ESI) calcd for C 12 H 17 O5S + [M+H] + 273.0791, found 273.0790.

[0124] Example 22

[0125]

[0126] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 4-bromobenzyl sulfone (0.2 mmol), glycoside S20 (1.0 mmol), G (0.04 mmol), potassium phosphate (0.24 mmol), and ethyl acetate (2.0 mL) were added to a reaction tube equipped with a magnetic dome. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 22 (31.8 mg, 55% yield, α / β > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, Methanol-d4) δ 7.99 –7.92 (m, 2H), 7.72 – 7.66 (m, 2H), 5.23 (dd, J = 19.6, 4.7 Hz, 1H, anomericH), 4.88 (ddd, J = 53.9, 4.7, 3.9 Hz, 1H), 4.40 (ddd, J = 18.5, 5.3, 3.9 Hz,1H), 4.15 – 4.11 (m, 1H), 3.80 – 3.70 (m, 2H), 3.12 (s, 3H). 13 C NMR (151 MHz, Methanol-d4) δ 146.1 (d, J = 5.9 Hz), 140.0, 127.3, 126.4, 102.9 (d, J =187.7 Hz), 85.1 (d, J = 5.7 Hz), 82.0 (d, J = 26.5 Hz), 75.4 (d, J = 23.4Hz), 61.4 (d, J = 1.5 Hz), 43.0. 19 F NMR (565 MHz, Methanol-d4) δ -188.60 (dt,J = 54.1, 19.1 Hz). HRMS: (ESI) calcd for C 12 H 16 FO5S + [M+H] + 291.0697, found291.0691.

[0127] Example 23

[0128]

[0129] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 4-bromobenzyl sulfone (0.2 mmol), glycoside S21 (1.0 mmol), G (0.04 mmol), potassium phosphate (0.24 mmol), and ethyl acetate (2.0 mL) were added to a reaction tube equipped with a magnetic dome. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 23 (26.4 mg, 46% yield, α / β = 17 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, Methanol-d4) δ 7.99 –7.95 (m, 2H), 7.73 – 7.69 (m, 2H), 5.13 (dd, J = 5.7, 2.9 Hz, 1H, anomericH), 3.51 (ddd, J = 10.8, 8.1, 4.4 Hz, 1H), 3.30 – 3.28 (m, 1H), 3.14 – 3.09(m, 4H), 2.64 (ddd, J = 13.9, 4.5, 2.9 Hz, 1H), 2.02 (ddd, J = 13.9, 10.8,5.5 Hz, 1H), 1.31 (d, J = 6.3 Hz, 3H). 13 C NMR (151 MHz, Methanol-d4) δ 147.1,139.5, 127.4, 127.1, 76.9, 71.7, 71.0, 68.6, 43.0, 34.4, 16.8. HRMS: (ESI)calcd for C 13 H 19 O 5 S + [M+H] + 287.0945, found 287.0941.

[0130] Example 24

[0131]

[0132] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 4-bromobenzyl sulfone (0.2 mmol), glycoside S38 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), anhydrous acetonitrile (2.0 mL), and dimethyl sulfoxide (1 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 24 (16.9 mg, 28% yield, α / β > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, Methanol-d4) δ 7.96 (d, J = 8.2 Hz, 2H), 7.72 (d, J = 8.2 Hz, 2H), 4.97 (d, J= 4.6 Hz, 1H, anomeric H), 4.87 (s, 3H), 4.35 (dd, J = 4.6, 3.2 Hz, 1H), 3.63(t, J = 6.9 Hz, 1H), 3.59 (dd, J = 7.3, 3.2 Hz, 1H), 3.55 (p, J = 6.5 Hz,1H), 1.38 (d, J = 6.4 Hz, 3H). 13 C NMR (151 MHz, Methanol-d4) δ 145.5, 139.6,127.5, 127.2, 75.5, 72.7, 72.3, 71.4, 70.2, 22.7, 16.4. HRMS: (ESI) calcd forC 13 H 19 O6S + [M+H] + 303.0897, found 303.0892.

[0133] Example 25

[0134]

[0135] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.1 mmol), glycoside S22 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 25 (38.4 mg, 44% yield, β / α > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 7.95 – 7.90 (m,2H), 7.49 – 7.44 (m, 2H), 6.16 (d, J = 8.7 Hz, 1H), 5.75 (t, J = 2.9 Hz, 1H), 5.14 (dd, J = 8.7, 3.0 Hz, 1H), 5.03 (dd, J = 10.1, 2.7 Hz, 1H), 4.98 (d, J =10.1 Hz, 1H), 2.59 (s, 3H), 2.24 (s, 3H), 2.12 (s, 3H), 2.05 (s, 3H), 1.82(s, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.7, 169.9, 169.3, 169.1, 168.7, 141.0,137.4, 128.4, 127.4, 90.2, 74.5, 70.1, 68.6, 68.3, 26.7, 20.9, 20.8, 20.6,20.4. HRMS: (ESI) calcd for C 21 H 24 O 10 Na + [M+Na] + 459.1262, found 459.1264.

[0136] Example 26

[0137]

[0138] Under an argon atmosphere, ferric dibromide (0.02 mmol), (E)-1-(2-bromovinyl)-4-(methanesulfonyl)benzene (0.2 mmol), glycoside S11 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 26 (45.4 mg, 50% yield, α / β > 20 / 1, E / Z > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ7.87 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H), 6.79 (dd, J = 16.5, 1.9Hz, 1H), 6.39 (dd, J = 16.5, 4.6 Hz, 1H), 5.49 (t, J = 2.8 Hz, 1H), 5.15 –5.07 (m, 2H), 4.63 (dt, J = 4.5, 2.3 Hz, 1H, anomeric H), 3.83 (dq, J = 8.4,6.2 Hz, 1H), 3.02 (s, 3H), 2.14 (s, 3H), 2.01 (s, 3H), 2.00 (s, 3H), 1.25 (d,J = 6.2 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 170.3, 170.2, 169.7, 141.0, 139.7,132.2, 128.0, 127.7, 127.3, 74.8, 71.0, 70.4, 69.3, 69.2, 44.4, 20.9, 20.7,20.6, 17.5. HRMS: (ESI) calcd for C 21 H 27 O9S + [M+H] + 455.1370, found 455.1371.

[0139] Example 27

[0140]

[0141] Under an argon atmosphere, ferric dibromide (0.02 mmol), 1-(2,2-difluorovinyl)-4-(methanesulfonyl)benzene (0.2 mmol), glycoside S11 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 27 (36.8 mg, 39% yield, α / β > 20 / 1, E / Z > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ7.92 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.5 Hz, 2H), 6.06 (d, J = 38.4 Hz, 1H), 5.65 (t, J = 3.2 Hz, 1H), 5.25 (dd, J = 9.1, 3.3 Hz, 1H), 5.13 (t, J =8.7 Hz, 1H), 4.67 (dd, J = 8.9, 2.7 Hz, 1H, anomeric H), 3.92 (dq, J = 7.2,6.8 Hz, 1H), 3.06 (s, 3H), 2.17 (s, 3H), 2.06 (d, J = 6.8 Hz, 6H), 1.32 (d, J= 6.3 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 170.3, 170.1, 169.8, 156.6 (d, J =276.5 Hz), 139.5 (d, J = 2.2 Hz), 137.3 (d, J = 2.4 Hz), 129.7 (d, J = 7.7Hz), 127.7, 109.1 (d, J = 5.6 Hz), 73.5 (d, J = 26.5 Hz), 70.7 (d, J = 23.5Hz), 69.5, 67.9 (d, J = 3.6 Hz), 44.5, 20.9, 20.8, 20.7, 17.5. 19 F NMR (565MHz, CDCl3) δ -107.44 (dd, J = 38.5, 9.4 Hz). HRMS: (ESI) calcd for C 21 H 29 FO9SN + [M+NH4] +490.1542, found 490.1544.

[0142] Example 28

[0143]

[0144] Under an argon atmosphere, ferric bromide (0.01 mmol), 1-(2,2-difluorovinyl)-4-(methanesulfonyl)benzene (0.1 mmol), glycoside S23 (0.5 mmol), E (0.002 mmol), potassium phosphate (0.12 mmol), and anhydrous acetonitrile (1.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 28 (25.4 mg, 31% yield, α / β > 20 / 1, E / Z > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ7.93 (d, J = 8.5 Hz, 2H), 7.70 (d, J = 8.5 Hz, 2H), 6.07 (d, J = 38.8 Hz,1H), 5.40 – 5.35 (m, 2H), 5.29 (dd, J = 6.2, 4.3 Hz, 1H), 5.23 – 5.20 (m,1H), 5.07 (t, J = 9.8 Hz, 1H), 4.94 (dd, J = 10.5, 3.9 Hz, 1H), 4.84 (dd, J =11.0, 5.4 Hz, 1H, anomeric H), 4.43 (dd, J = 11.8, 2.3 Hz, 1H), 4.25 – 4.19(m, 3H), 4.13 – 4.08 (m, 2H), 3.76 (dd, J = 7.9, 4.3 Hz, 1H), 3.06 (s, 3H), 2.16 (s, 3H), 2.10 (s, 6H), 2.09 (s, 3H), 2.07 (s, 3H), 2.02 (s, 3H), 1.99 (s, 3H). 13C NMR (151 MHz, CDCl3) δ 170.6, 170.4, 170.3, 170.0, 169.9, 169.6,169.4, 157.4 (d, J = 275.0 Hz), 145.5 (d, J = 2.1 Hz), 139.3, 137.6, 129.5(d, J = 7.2 Hz), 127.7, 108.2 (d, J = 3.5 Hz), 96.6, 74.4, 72.6, 70.6, 70.5,70.4, 69.8, 69.4, 68.5, 68.1, 67.8, 44.5, 20.9, 20.8, 20.7, 20.63, 20.58, 20.55, 20.5. 19 F NMR (565 MHz, CDCl3) δ -109.08 – -109.41 (m). HRMS: (ESI)calcd for C 35 H 44 FO 19 S + [M+H] + 819.2176 was found; 819.2179 was also found.

[0145] Example 29

[0146]

[0147] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), 3-(bromoethynyl)pyridine (0.2 mmol), glycoside S11 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 29 (50.2 mg, 67% yield, α / β > 20 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 8.72 (d,J = 1.6 Hz, 1H), 8.58 (dd, J = 4.9, 1.4 Hz, 1H), 7.78 (dt, J = 7.9, 1.8 Hz,1H), 7.28 (dd, J = 7.8, 4.9 Hz, 1H), 5.46 (dd, J = 10.0, 3.4 Hz, 1H), 5.43 (dd, J = 3.4, 2.1 Hz, 1H), 5.09 (d, J = 9.8 Hz, 1H), 4.92 (d, J = 1.9 Hz, 1H,anomeric H), 4.10 (dq, J = 9.8, 6.1 Hz, 1H), 2.18 (s, 3H), 2.06 (s, 3H), 2.01(s, 3H), 1.28 (d, J = 6.2 Hz, 3H). 13 C NMR (151 MHz, CDCl3) δ 170.2, 170.0,169.9, 152.5, 149.5, 139.0, 123.0, 118.6, 86.5, 85.2, 71.3, 70.9, 69.9, 69.5,67.3, 20.9, 20.8, 20.7, 17.6. HRMS: (ESI) calcd for C 19 H 22 NO7 + [M+H] + 376.1390, found 376.1381.

[0148] Example 30

[0149]

[0150] Under an argon atmosphere, 1-(bromoethynyl)-4-(methanesulfonyl)benzene (0.1 mmol), glycoside S17 (0.5 mmol), E (0.002 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 30 (48.8 mg, 66% yield, α / β > 20 / 1) was obtained by column chromatography. 1H NMR (600 MHz, CDCl3) δ 7.93 (d, J = 8.4 Hz, 2H), 7.70 (d, J = 8.4Hz, 2H), 5.58 (d, J = 4.0 Hz, 1H), 5.41 (t, J = 10.0 Hz, 1H), 5.26 (ddd, J =11.3, 8.8, 5.0 Hz, 1H,), 5.08 (t, J = 9.9 Hz, 1H), 5.01 (dd, J = 5.6, 1.8 Hz,1H, anomeric H), 4.88 (dd, J = 10.5, 4.1 Hz, 1H), 4.45 (dd, J = 12.2, 2.4 Hz,1H), 4.30 (dd, J = 12.2, 4.1 Hz, 1H), 4.25 (dd, J = 12.5, 3.4 Hz, 1H), 4.17 –4.13 (m, 1H), 4.07 (dd, J = 12.5, 2.1 Hz, 1H), 3.98 (dt, J = 10.3, 2.8 Hz,1H), 3.89 (t, J = 9.1 Hz, 1H), 3.06 (s, 3H), 2.37 (ddd, J = 12.8, 4.9, 1.5Hz, 1H), 2.15 (s, 3H), 2.10 (s, 3H), 2.05 (s, 3H), 2.02 (s, 3H), 2.01 (s,3H), 2.00 (s, 3H), 1.92 – 1.84 (m, 1H). 13 C NMR (151 MHz, CDCl3) δ 170.6,170.5, 170.3, 170.10, 170.09, 169.4, 140.4, 132.8, 127.7, 127.5, 95.7, 88.6,86.6, 73.3, 73.1, 71.7, 70.1, 69.5, 68.4, 67.9, 64.0, 63.2, 61.4, 44.5, 34.9,21.2, 20.9, 20.7, 20.62, 20.57, 20.5. HRMS: (ESI) calcd for C 33 H 41 O 17 S + [M+H] + 741.2059, found 741.2054.

[0151] Example 31

[0152]

[0153] Under an argon atmosphere, (8R,9S,10R,13S,14S,17S)-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13,14,15,16,17-tetradecano-1H-cyclopenta[a]phenanthrene-17-yl acrylate (0.1 mmol), glycoside S2 (0.2 mmol), E (0.004 mmol), acetonitrile (1.0 mL), and H2O (100 μL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 31 (34.3 mg, 57% yield, β / α > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 5.13 (t, J = 5.4 Hz, 1H), 4.92 (t, J = 5.9Hz, 1H), 4.59 (dd, J = 9.2, 7.8 Hz, 1H), 4.29 (dd, J = 11.6, 2.8 Hz, 1H), 4.16 – 4.07 (m, 2H), 3.99 (ddd, J = 8.2, 6.0, 4.3 Hz, 1H, anomeric H), 2.47 – 2.37 (m, 4H), 2.35 – 2.33 (m, 1H), 2.28 – 2.25 (m, 1H), 2.18 – 2.14 (m, 1H),2.09 (s, 3H), 2.06 (s, 6H), 2.03 – 1.99 (m, 2H), 1.86 – 1.80 (m, 2H), 1.79 –1.74 (m, 2H), 1.69 – 1.64 (m, 2H), 1.59 – 1.54 (m, 2H), 1.43 – 1.31 (m, 3H), 1.18 (s, 3H), 1.07 – 0.98 (m, 3H), 0.96 – 0.91 (m, 1H), 0.82 (s, 3H). 13C NMR (151 MHz, CDCl3) δ 199.5, 172.8, 170.9, 170.6, 169.84, 169.81, 124.0, 82.6,79.9, 79.2, 73.9, 71.7, 63.5, 53.7, 50.2, 42.5, 38.6, 36.6, 35.7, 35.4, 33.9,32.7, 31.5, 30.2, 28.2, 27.5, 23.5, 20.8, 20.61, 20.60, 20.5, 17.4, 12.1.HRMS: (ESI) calcd for C 33 H 47 O 10 + [M+H] + 603.3164 was found; 603.3165 was also found.

[0154] Example 32

[0155]

[0156] Under an argon atmosphere, 4-oxocyclohexyl acrylate (0.2 mmol), glycoside S11 (0.4 mmol), E (0.004 mmol), acetonitrile (1.0 mL), and H2O (100 μL) were added to a reaction tube equipped with a magnetic dome. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 32 (48.6 mg, 55% yield, α / β > 20 / 1) was obtained by column chromatography. 1 H NMR(600 MHz, CDCl3) δ 5.17 (ddd, J = 16.8, 7.5, 3.3 Hz, 3H), 5.01 (t, J = 8.4Hz, 1H), 3.91 (dt, J = 10.9, 3.5 Hz, 1H, anomeric H), 3.79 – 3.75 (m, 1H),2.55 – 2.51 (m, 2H), 2.49 – 2.42 (m, 2H), 2.38 – 2.33 (m, 2H), 2.11 (s, 3H),2.08 – 2.04 (m, 8H), 2.01 (s, 3H), 1.90 (dtd, J = 15.0, 7.7, 4.0 Hz, 1H),1.23 (d, J = 6.3 Hz, 3H). 13C NMR (151 MHz, CDCl3) δ 209.6, 172.0, 170.2,170.0, 169.8, 73.7, 71.3, 70.8, 69.0, 68.9, 68.3, 37.22, 37.21, 30.45, 30.36,23.9, 20.9, 20.8, 20.7, 17.5. HRMS: (ESI) calcd for C 21 H 31 O 10 + [M+H] + 443.1912, found 443.1916.

[0157] Example 33

[0158]

[0159] Under an argon atmosphere, acrylonitrile (0.2 mmol), glycoside S15 (0.4 mmol), E (0.004 mmol), acetonitrile (2.0 mL), and H2O (200 μL) were added to a reaction tube containing a magnetic dome. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). Product 33 (49.1 mg, 75% yield, α / β = 13 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ 5.03 (td, J = 6.3, 4.1 Hz, 1H), 4.79 (t, J = 5.4 Hz, 1H), 4.53 (dd,J = 12.0, 7.5 Hz, 1H), 4.13-4.02 (m, 2H), 3.93 (dt, J = 8.2, 4.2 Hz, 1H),2.46 – 2.41 (m, 2H), 2.07 (s, 3H), 2.06 (d, J = 0.7 Hz, 6H), 2.01 – 1.98 (m,1H), 1.90 (ddd, J = 13.9, 7.2, 4.1 Hz, 1H), 1.83 (ddd, J = 14.0, 6.7, 4.1 Hz,1H), 1.80 – 1.73 (m, 1H). 13C NMR (151 MHz, CDCl3) δ 170.6, 169.6, 169.5,119.1, 71.9, 67.7, 67.4, 66.6, 61.0, 31.9, 29.0, 20.9, 20.8, 20.7, 13.5.HRMS: (ESI) calcd for C 15 H 21 NO7Na + [M+Na] + 350.1210, found 350.1207.

[0160] Example 34

[0161]

[0162] Under an argon atmosphere, methyl (S)-2-acrylamido-2-phenylacetate (0.1 mmol), glycoside S17 (0.2 mmol), E (0.004 mmol), acetonitrile (1.0 mL), and H2O (100 μL) were added to a reaction tube equipped with a magnetic dome. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm) irradiation. The product 34 (57.1 mg, 73% yield, α / β >20 / 1) was obtained by column chromatography. 11H NMR (600 MHz, CDCl3) δ 7.41 – 7.30 (m, 5H), 6.82 (d, J = 7.3 Hz, 1H), 5.57 (d, J = 7.2 Hz, 1H), 5.41 (t, J = 9.9 Hz, 1H), 5.37 (d, J = 3.9 Hz, 1H), 5.04 (t, J = 9.8 Hz, 1H), 4.98 – 4.94 (m, 1H), 4.87 (dd, J = 10.4, 3.9 Hz, 1H), 4.48 (dd, J = 11.9, 7.1 Hz, 1H), 4.18 (ddd, J = 17.6, 12.1, 4.1 Hz, 2H), 4.11 (dd, J = 12.4, 2.3 Hz, 1H), 4.09 – 3.97 (m, 3H), 3.71 (s, 3H), 3.65 (t, J = 5.4 Hz, 1H), 2.40 – 2.32 (m, 2H), 2.15 – 2.04 (m, 10H), 2.03 – 1.98 (m, 9H), 1.96 – 1.93 (m, 1H), 1.85 (ddt, J = 14.5, 7.9, 4.0 Hz, 1H), 1.71 (ddd, J = 13.8, 6.9, 4.1 Hz, 1H). 13 13C NMR (151 MHz, CDCl3) δ 172.0, 171.5, 170.7, 170.6, 170.2, 170.0, 169.9, 169.6, 136.3, 129.0, 128.6, 127.4, 96.1, 73.1, 72.0, 70.3, 70.1, 69.7, 68.24, 68.20, 67.3, 62.4, 61.7, 56.5, 52.7, 31.94, 31.86, 28.8, 21.1, 20.74, 20.68, 20.64, 20.57, 20.5. HRMS: (ESI) calcd for C 36 H 48 NO 18 + [M+H] + 782.2865, found 782.2863.

[0163] Example 35

[0164]

[0165] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), F (0.03 mmol), p-bromoacetophenone (0.1 mmol), glycoside S24 (0.5 mmol), E (0.004 mmol), potassium phosphate (0.12 mmol), and anhydrous acetonitrile (1.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 96 hours under ultraviolet light (10 W, 390 nm). The product 35 (20.7 mg, 75% yield, dr > 20 / 1, rr = 10 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3)δ 7.96 – 7.92 (m, 2H), 7.51 – 7.46 (m, 2H), 4.87 (d, J = 5.2 Hz, 1H, anomericH), 4.51 (dd, J = 7.0, 5.3 Hz, 1H), 4.37 (dd, J = 7.0, 4.8 Hz, 1H), 4.17 –4.12 (m, 1H), 2.60 (s, 3H), 1.62 (s, 3H), 1.43 (d, J = 6.4 Hz, 3H), 1.35 (s,3H). 13 C NMR (151 MHz, CDCl3) δ 197.8, 145.2, 136.5, 128.5, 125.7, 115.4,87.2, 86.2, 85.0, 80.6, 27.4, 26.6, 25.5, 18.9. HRMS: (ESI) calcd for C 16 H 21 O4 + [M+H] + 277.1434, found 277.1440.

[0166] Example 36

[0167]

[0168] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), F (0.03 mmol), 1-bromo-4-(methanesulfonyl)benzene (0.1 mmol), glycoside S27 (0.5 mmol), E (0.004 mmol), potassium phosphate (0.12 mmol), and anhydrous acetonitrile (1.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 96 hours under ultraviolet light (10 W, 390 nm). The product 36 (50.9 mg, 87% yield, dr > 20 / 1, rr = 15 / 1) was obtained by column chromatography. 1 H NMR (600MHz, CDCl3) δ 7.90 (d, J = 8.4 Hz, 2H), 7.62 (dd, J = 7.9, 1.3 Hz, 6H), 7.50– 7.45 (m, 5H), 7.40 (t, J = 7.4 Hz, 6H), 5.28 (d, J = 4.2 Hz, 1H, anomericH), 4.94 (d, J = 5.9 Hz, 1H), 4.86 (dd, J = 5.8, 4.4 Hz, 1H), 4.37 (t, J =3.5 Hz, 1H), 4.05 (dd, J = 11.1, 3.7 Hz, 1H), 3.96 (dd, J = 11.1, 3.7 Hz,1H), 3.05 (s, 3H), 1.37 (s, 3H), 1.25 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ143.6, 135.3, 133.3, 130.4, 128.08, 128.05, 126.9, 112.7, 84.4, 83.6, 83.3,82.8, 65.5, 44.6, 26.0, 24.6. HRMS: (ESI) calcd for C 33 H 35 O6SSi + [M+H] + 587.1918, found 587.1919.

[0169] Example 37

[0170]

[0171] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.04 mmol), F (0.06 mmol), p-bromoacetophenone (0.2 mmol), glycoside S27 (1.0 mmol), E (0.008 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic dome. The reaction was carried out at 25 °C for 96 hours under ultraviolet light (10 W, 390 nm). The product 37 (51.5 mg, 77% yield, dr > 20 / 1, rr = 5 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3)δ 7.93 (d, J = 8.3 Hz, 2H), 7.46 (d, J = 8.2 Hz, 2H), 4.96 (d, J = 5.0 Hz,1H, anomeric H), 4.63 (dd, J = 6.7, 4.1 Hz, 1H), 4.51 (dd, J = 6.7, 5.1 Hz, 1H), 4.40 (dd, J = 11.9, 3.7 Hz, 1H), 4.33 (q, J = 4.0 Hz, 1H), 4.22 (dd, J =11.9, 5.0 Hz, 1H), 2.58 (s, 3H), 2.03 (s, 3H), 1.62 (s, 3H), 1.35 (s, 3H). 13 CNMR (151 MHz, CDCl3) δ 197.7, 170.6, 144.9, 136.6, 128.5, 125.5, 115.2, 86.8,85.5, 81.9, 81.9, 64.1, 27.4, 26.6, 25.5, 20.7. HRMS: (ESI) calcd for C 18 H 23 O6 + [M+H] + 335.1495, found 335.1492.

[0172] Example 38

[0173]

[0174] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.04 mmol), F (0.06 mmol), p-bromoacetophenone (0.2 mmol), glycoside S26 (1.0 mmol), E (0.008 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 96 hours under ultraviolet light (10 W, 390 nm). The product 38 (39.1 mg, 67% yield, dr > 20 / 1, rr = 15 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3)δ 7.95 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 8.2 Hz, 2H), 4.92 (d, J = 5.5 Hz,1H, anomeric H), 4.75 (dd, J = 6.9, 4.3 Hz, 1H), 4.51 (dd, J = 6.9, 5.5 Hz,1H), 4.20 (q, J = 4.1 Hz, 1H), 3.95 (d, J = 12.0 Hz, 1H), 3.85 – 3.78 (m,1H), 2.60 (s, 3H), 1.98 (s, 1H), 1.63 (s, 3H), 1.36 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.8, 144.7, 136.6, 128.6, 125.7, 115.3, 86.7, 85.3, 84.5, 81.4,62.8, 27.5, 26.6, 25.4. HRMS: (ESI) calcd for C 16 H 21 O5 + [M+H] + 293.1384, found 293.1382.

[0175] Example 39

[0176]

[0177] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.04 mmol), F (0.06 mmol), p-bromoacetophenone (0.2 mmol), glycoside S29 (1.0 mmol), E (0.008 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 96 hours under ultraviolet light (10 W, 390 nm). The product 39 (52.9 mg, 63% yield, dr > 20 / 1, rr = 16 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3)δ 7.91 (d, J = 8.2 Hz, 2H), 7.50 (d, J = 8.3 Hz, 2H), 6.16 (s, 1H), 4.92 (d,J = 7.6 Hz, 1H), 4.60 (d, J = 2.2 Hz, 2H), 0.95 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.7, 169.2,143.3, 136.9, 128.1, 127.7, 113.0, 110.6, 100.9, 85.4, 82.7, 81.4, 80.0,78.8, 27.22, 27.19, 26.6, 25.6, 24.3, 21.0. HRMS: (ESI) calcd for C 22 H 32 O8N + [M+NH4] + 438.2122, found 438.2115.

[0178] Example 40

[0179]

[0180] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S32 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 40 (60.8 mg, 84% yield, dr > 20 / 1, rr > 20 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ7.94 (d, J = 8.2 Hz, 2H), 7.47 (d, J = 8.2 Hz, 2H), 4.81 (d, J = 7.5 Hz, 1H,anomeric H), 4.40 (t, J = 7.1 Hz, 1H), 4.33 (t, J = 6.9 Hz, 1H), 4.20 (dd, J= 10.9, 7.2 Hz, 1H), 3.94 (dd, J = 11.0, 5.5 Hz, 1H), 3.76 (t, J = 10.6 Hz,1H), 3.55 (td, J = 10.5, 5.5 Hz, 1H), 2.57 (s, 3H), 1.55 (d, J = 8.8 Hz, 6H), 1.42 (s, 3H), 1.34 (s, 3H). 13 C NMR (151 MHz, CDCl3) δ 197.6, 144.1, 136.9,128.5, 127.3, 110.1, 99.5, 77.3, 76.3, 75.3, 72.3, 65.1, 63.0, 29.0, 27.5,26.7, 25.0, 19.0. HRMS: (ESI) calcd for C 20 H 27 O6 + [M+H] + 363.1802, found 363.1800.

[0181] Example 41

[0182]

[0183] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S33 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 41 (52.9 mg, 76% yield, dr > 20 / 1, rr > 20:1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ7.94 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H), 5.10 (t, J = 5.7 Hz, 1H), 4.81 (d, J = 7.0 Hz, 1H, anomeric H), 4.31 (dd, J = 7.0, 5.8 Hz, 1H), 4.25(t, J = 5.7 Hz, 1H), 3.88 (p, J = 6.6 Hz, 1H), 2.58 (s, 3H), 2.11 (s, 3H),1.60 (s, 3H), 1.36 (s, 3H), 1.35 (d, J = 6.7 Hz, 3H). 13 C NMR (151 MHz, CDCl3)δ 197.6, 169.9, 144.7, 136.5, 128.4, 126.7, 109.8, 76.1, 75.4, 72.6, 72.1,70.1, 27.8, 26.6, 25.8, 21.0, 16.7. HRMS: (ESI) calcd for C 19 H 25 O6 + [M+H] + 349.1645, found 349.1637.

[0184] Example 42

[0185]

[0186] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S35 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic ball. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The product 42 (52.1 mg, 72% yield, dr > 20 / 1, rr = 14 / 1) was obtained by column chromatography. 1 H NMR (600 MHz, CDCl3) δ7.95 – 7.91 (m, 2H), 7.44 – 7.40 (m, 2H), 5.69 (d, J = 2.9 Hz, 1H), 5.26 (s,1H, H4), 5.24 (s, 1H), 4.33 (q, J = 1.5 Hz, 1H), 4.25 – 4.21 (m, 1H), 4.16 (dd, J = 6.3, 3.0 Hz, 1H), 2.59 (s, 3H), 2.12 (s, 3H), 1.58 (s, 3H), 1.36 (s,3H). 13 C NMR (151 MHz, CDCl3) δ 197.7, 169.9, 145.9, 136.8, 128.6, 126.0,110.5, 100.8, 80.1, 76.6, 73.8, 71.6, 70.3, 26.7, 26.0, 25.8, 21.0. HRMS:(ESI) calcd for C 19 H 23 O7 + [M+H] + 363.1444, found 363.1449.

[0187] Comparative Example 1

[0188]

[0189] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), ligand (i.e., the structure shown in the formula ligand) (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S1 (1.0 mmol), E (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm). The expected product 1 was not detected.

[0190] Comparative Example 2

[0191]

[0192] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S1 (1.0 mmol), photocatalyst (Ir[dF(CF3)ppy]2(dtbbpy)PF6) (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm), and only <5% of the expected product 2 was formed.

[0193] Comparative Example 3

[0194]

[0195] Under an argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), D (0.03 mmol), p-bromoacetophenone (0.2 mmol), glycoside S1 (1.0 mmol), photocatalyst (4CzIPN) (0.004 mmol), potassium phosphate (0.24 mmol), and anhydrous acetonitrile (2.0 mL) were added to a reaction tube equipped with a magnetic field. The reaction was carried out at 25 °C for 60 h under ultraviolet light (10 W, 390 nm), and only <5% of the expected product 3 was formed.

[0196] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for synthesizing functionalized carbon glycosides, characterized in that, The mixture of materials including coupling reagent, glycoside, photocatalyst, metal catalyst, ligand, base and solvent is mixed and reacted completely under ultraviolet light to obtain functionalized carbon glycoside. The coupling reagent is selected from one of the following structures: ； The glycoside is selected from one of the following structures: ； ； ； ； ； The photocatalyst is selected from one of the following structures: ； The metal catalyst is selected from one of nickel chloride, nickel bromide, nickel chloride ethylene glycol dimethyl ether, nickel bromide ethylene glycol dimethyl ether, cyclooctadiene nickel, nickel acetylacetone, nickel iodide, nickel acetate tetrahydrate, and ferric dibromide; The ligand is selected from one of the following structures: 。 2. The method for synthesizing a functionalized carbon glycoside according to claim 1, characterized in that, The metal catalyst is nickel bromide ethylene glycol dimethyl ether or iron dibromide.

3. The method for synthesizing a functionalized carbon glycoside according to claim 1, characterized in that, The reaction temperature was 25℃, and the reaction time was 48~60 h.

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