Synthetic method of functionalized carbon glycoside

Abstract

The invention discloses a synthetic method of functionalized carbon glycoside, and belongs to the technical field of organic synthesis. Coupling reagents (aryl bromide, alkenyl bromide, alkenyl gem-difluoride, alkynyl bromide and electron-deficient olefin) and glucoside are used as substrates, and are subjected to complete reaction under ultraviolet irradiation through catalysis of a photocatalyst or synergistic catalysis of the photocatalyst and a metal catalyst, and the compound is obtained. The carbon glycosides are functionalized (arylated, alkenylated, alkenyl monofluorinated, alkynylated and alkylated). According to the method, the stereoselective functionalization reaction of the glucoside C (sp3)-H bond is realized by utilizing a photocatalysis or light-metal concerted catalysis strategy, and the method is mild in condition and wide in substrate adaptability; besides, the method takes simple and stable glucoside as a raw material, and also has the advantages of low cost, high atom utilization rate and economical steps, and the synthesized functionalized carbon glucoside can realize synthesis of various natural products and commercially available drugs through subsequent conversion, and has huge synthesis value.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for synthesizing functionalized carbon glycoside. Background Art

[0002] Compared with oxygen glycosides, carbon glycosides have higher stability and better drugability. Carbon glycosylation has become an effective strategy for glycoconjugate drug modification. The efficient synthesis of carbon glycosides has received increasing attention in the fields of sugar chemistry and pharmaceutical research and development. It belongs to the frontier field of chemistry and its interdisciplinary sciences and is a major national strategic need in the field of life and health.

[0003] Due to the diversity of sugars and the complexity of their structures, and the lack of a unified synthesis method, how to efficiently synthesize carbon glycosides has always been a challenge in the field of sugar chemistry. Traditional methods for synthesizing carbon glycosides include Friedel-Crafts-type glycosidation reactions between electron-rich aromatic hydrocarbons and sugar donors, or coupling metal reagents with sugar donors to construct carbon glycosidic bonds. These methods have limitations such as low efficiency, poor selectivity, and poor atom economy. Therefore, the development of efficient and highly stereoselective methods for synthesizing carbon glycosides is of great significance to the field of sugar chemistry and pharmaceutical research and development. Summary of the invention

[0004] In view of the above deficiencies in the prior art, the present invention provides a method for synthesizing functionalized carbon glycosides, which utilizes photocatalysis or light-metal synergistic catalysis to site-selectively activate glycoside CH bonds to efficiently synthesize functionalized carbon glycosides. The synthesized carbon glycosides can be used to synthesize a variety of commercially available drugs through subsequent conversion, and have great synthetic value.

[0005] To achieve the above purpose, the specific technical solutions of the present invention are as follows:

[0006] A method for synthesizing a functionalized carbon glycoside comprises the following steps: mixing materials including a coupling reagent A, a glycoside B, and a photocatalyst with a solvent under an inert atmosphere, and reacting them completely under ultraviolet light irradiation to obtain a functionalized carbon glycoside C; wherein the coupling reagent A is one of an aryl bromide, an alkenyl bromide, an alkenyl geminal difluoride, an alkynyl bromide, and an electron-deficient olefin.

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

[0008]

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

[0010]

[0011] The derivative of glucose or mannose 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 comprises one or more of a metal catalyst, a ligand, and a base, and different reaction conditions can be selected according to different coupling reagents. For example, when the coupling reagent is an aryl bromide, a photocatalyst and a metal catalyst need to work together, as well as suitable ligands and bases, in order to react completely with the glycoside; when the coupling reagent is an alkenyl bromide or an alkenyl geminal difluoride, a photocatalyst and a metal catalyst need to work together, as well as suitable bases, in order to react completely with the glycoside; when the coupling reagent is an alkynyl bromide, a photocatalyst needs to be combined with a suitable base in order to react completely with the glycoside; when the coupling reagent is an electron-deficient olefin, only a photocatalyst needs to be added to react completely 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 dimethyl ether, nickel bromide dimethyl ether, cyclooctadiene nickel, nickel acetylacetonate, nickel perchlorate, nickel iodide, nickel acetate tetrahydrate, and ferric dibromide.

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

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

[0025]

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

[0027] Preferably, the base 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 base is potassium phosphate.

[0029] Preferably, the solvent includes but is not limited to a mixed solvent consisting 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] The present invention uses coupling reagents (aryl bromides, alkenyl bromides, alkenyl geminal difluorides, alkynyl bromides, electron-deficient olefins) and glycosides as substrates to react and obtain functionalized carbon glycosides. First, the carbon-hydrogen bond of the glycoside is directly broken by a visible light-promoted hydrogen atom transfer (HAT) process to generate glycoside free radicals, and then the glycoside free radicals are coupled with coupling reagents (aryl bromides, alkenyl bromides, alkenyl geminal difluorides, alkynyl bromides, electron-deficient olefins). Alternatively, under the coordinated catalysis of a metal catalyst, the glycoside free radicals are coupled with coupling reagents (aryl bromides, alkenyl bromides, alkenyl geminal difluorides, alkynyl bromides, electron-deficient olefins) to achieve glycoside C (sp 3 )-H bond stereoselective functionalization reaction to obtain functionalized carbon glycoside compounds. The present invention utilizes a simple photocatalytic or light-metal synergistic catalytic strategy to achieve stereoselective functionalization of glycoside carbon-hydrogen bonds, such as arylation, alkenylation, alkenyl monofluorination, alkynylation and alkylation. The synthesized carbon glycoside can be used to synthesize a variety of commercially available drugs through subsequent transformation, and has great synthetic value.

[0034] Compared with the prior art, the present invention is beneficial in that:

[0035] 1. The present invention provides a method for directly breaking the carbon-hydrogen bond of glycosides by utilizing photo-promoted hydrogen atom transfer and metal-coordinated catalysis to achieve enantioselective functionalization (arylation, alkenylation, alkenyl monofluorination, alkynylation and alkylation) to prepare a series of carbon glycoside compounds.

[0036] 2. The method of the present invention has mild reaction conditions, good functional group tolerance, and a wide range of substrate applications. It is an efficient, green, and inexpensive method for synthesizing carbon glycosides. In addition, the present invention directly uses simple and stable glycosides as raw materials, avoiding the use of precious metal catalysts and equivalent redox reagents, thereby greatly reducing the synthesis cost. DETAILED DESCRIPTION

[0037] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] The invention provides a method for synthesizing a functionalized carbon glycoside. The method comprises the following steps: mixing materials including a coupling reagent A, a glycoside B and a photocatalyst with a solvent under an inert atmosphere, and reacting the materials under ultraviolet light to obtain a functionalized carbon glycoside C; wherein the coupling reagent A is one of an aryl bromide, an alkenyl bromide, an alkenyl geminal difluoride, an alkynyl bromide and an electron-deficient olefin.

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

[0040]

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

[0042]

[0043] The derivative of glucose or mannose 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 further 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 dimethyl ether, nickel bromide dimethyl ether, cyclooctadiene nickel, nickel acetylacetonate, 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 base 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 mixed solvent consisting of one or more of acetonitrile, acetone, water, and dimethyl sulfoxide.

[0060] In the following specific examples, 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"-terpyridine, and G is (4-methoxyphenyl)(4-(trifluoromethyl)phenyl)methanone. All materials and solvents used are commercially available.

[0061] Example 1

[0062]

[0063] Under argon atmosphere, nickel bromide 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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. The 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 argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (10 W, 390 nm). The 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 argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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 argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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 7S + [M+H] + 357.1002, found357.1004.

[0073] Example 5

[0074]

[0075] Under argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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 argon atmosphere, nickel bromide dimethyl ether (0.02 mmol), D (0.03 mmol), 5-bromo-2-furoic acid methyl ester (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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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 argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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 argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (10 W, 390 nm). The 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 argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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] Embodiment 11

[0092]

[0093] Under argon atmosphere, nickel bromide 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 electron. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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 argon atmosphere, nickel bromide 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 electron. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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 8Na + [M+Na] + 443.1676, found 443.1666.

[0097] Embodiment 13

[0098]

[0099] Under argon atmosphere, nickel bromide 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 electron. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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 O7 + [M+Na] + 443.2040, found 443.2026.

[0100] Embodiment 14

[0101]

[0102] Under argon atmosphere, nickel bromide 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 electron. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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 O7 + [M+Na] + 415.1727, found 415.1718.

[0103] Embodiment 15

[0104]

[0105] Under argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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 argon atmosphere, nickel bromide 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 electron. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 17

[0110]

[0111] Under argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 18

[0113]

[0114] Under 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 electron. The mixture was reacted at 25 °C for 60 hours under irradiation with a violet lamp (10 W, 390 nm), concentrated, and flash column chromatography was performed to obtain 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] Embodiment 19

[0116]

[0117] Under argon atmosphere, nickel bromide 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 electron. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 20

[0119]

[0120] Under argon atmosphere, nickel bromide 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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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 argon atmosphere, nickel bromide 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 bar. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 22

[0125]

[0126] Under argon atmosphere, nickel bromide 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 electron. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 23

[0128]

[0129] Under argon atmosphere, nickel bromide dimethyl ether (0.02 mmol), D (0.03 mmol), 4-bromophenyl 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 bar. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 24

[0131]

[0132] Under argon atmosphere, nickel bromide 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 magnet. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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] Embodiment 25

[0134]

[0135] Under argon atmosphere, nickel bromide 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 electron. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 26

[0137]

[0138] Under argon atmosphere, iron dibromide (0.02 mmol), (E)-1-(2-bromovinyl)-4-(methylsulfonyl)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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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 9S + [M+H] + 455.1370, found 455.1371.

[0139] Embodiment 27

[0140]

[0141] Under argon atmosphere, iron dibromide (0.02 mmol), 1-(2,2-difluorovinyl)-4-(methylsulfonyl)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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 28

[0143]

[0144] Under argon atmosphere, iron dibromide (0.01 mmol), 1-(2,2-difluorovinyl)-4-(methylsulfonyl)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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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, found 819.2179.

[0145] Embodiment 29

[0146]

[0147] Under 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 electron. The mixture was reacted at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 30

[0149]

[0150] Under argon atmosphere, 1-(bromoethynyl)-4-(methylsulfonyl)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 electron. The mixture was reacted at 25 °C for 60 h under irradiation with a purple lamp (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] Embodiment 31

[0152]

[0153] Under 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-tetradecahydro-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 bar. The reaction was carried out at 25 ℃ under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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, found 603.3165.

[0154] Embodiment 32

[0155]

[0156] Under 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 bar. The mixture was reacted at 25 ℃ for 60 h under irradiation with a purple lamp (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] Embodiment 33

[0158]

[0159] Under 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 equipped with a magnet. The reaction was carried out at 25°C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. The 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] Embodiment 34

[0161]

[0162] Under argon atmosphere, (S)-methyl 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 bar. The reaction was carried out at 25 ℃ under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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 argon atmosphere, nickel bromide 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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 96 h. 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] Embodiment 36

[0167]

[0168] Under argon atmosphere, nickel bromide ethylene glycol dimethyl ether (0.02 mmol), F (0.03 mmol), 1-bromo-4-(methylsulfonyl)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 magnet. The mixture was reacted at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 96 h. 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 6SSi + [M+H] + 587.1918, found 587.1919.

[0169] Embodiment 37

[0170]

[0171] Under 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 magnet. The mixture was reacted at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 96 h. 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] Embodiment 38

[0173]

[0174] Under argon atmosphere, nickel bromide 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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 96 h. 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] Embodiment 39

[0176]

[0177] Under argon atmosphere, nickel bromide 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 magnet. The mixture was reacted at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 96 h. 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] Embodiment 40

[0179]

[0180] Under argon atmosphere, nickel bromide 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 magnet. The reaction was carried out at 25 ℃ under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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, found363.1800.

[0181] Embodiment 41

[0182]

[0183] Under argon atmosphere, nickel bromide 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 magnet. The reaction was carried out at 25 ℃ under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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] Embodiment 42

[0185]

[0186] Under argon atmosphere, nickel bromide 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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. 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 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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. No expected product 1 was detected.

[0190] Comparative Example 2

[0191]

[0192] Under argon atmosphere, nickel bromide 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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. Only <5% of the expected product 2 was generated.

[0193] Comparative Example 3

[0194]

[0195] Under argon atmosphere, nickel bromide 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 magnet. The reaction was carried out at 25 °C under irradiation with a purple lamp (10 W, 390 nm) for 60 h. Only <5% of the expected product 3 was produced.

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

Claims

1. A method for synthesizing functionalized carbon glycosides, characterized in that: The materials including coupling reagent, glycoside and photocatalyst are mixed with solvent, and reacted completely under ultraviolet light to obtain functionalized carbon glycoside; wherein the coupling reagent is one of aryl bromide, alkenyl bromide, alkenyl geminal difluoride, alkynyl bromide and electron-deficient olefin.

2. A method for synthesizing a functionalized carbon glycoside according to claim 1, characterized in that: The coupling reagent is selected from one of the following structures: 。 3. A method for synthesizing a functionalized carbon glycoside according to claim 1, characterized in that: The glycoside is selected from one of 1-deoxyglycoside, a derivative of glucose or mannose, 2-deoxyglycoside, an unprotected glycoside, and a glycoside protected by a protecting group; wherein the 1-deoxyglycoside is selected from one of the following structures: ； The derivative of glucose or mannose is selected from one of the following structures: ； The 2-deoxyglycoside is selected from one of the following structures: ； The unprotected glycoside is selected from one of the following structures: ； The glycoside protected by the protecting group is selected from one of the following structures: 。 4. A method for synthesizing a functionalized carbon glycoside according to claim 1, characterized in that: The photocatalyst is selected from one of the following structures: 。 5. A method for synthesizing a functionalized carbon glycoside according to claim 1, characterized in that: The material also includes one or more of a metal catalyst, a ligand, and a base.

6. A method for synthesizing a functionalized carbon glycoside according to claim 5, characterized in that: 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 dimethyl ether, nickel bromide dimethyl ether, cyclooctadiene nickel, nickel acetylacetonate, nickel perchlorate, nickel iodide, nickel acetate tetrahydrate, and ferric dibromide.

7. A method for synthesizing a functionalized carbon glycoside according to claim 6, characterized in that: The metal catalyst is nickel bromide ethylene glycol dimethyl ether or ferric dibromide.

8. A method for synthesizing a functionalized carbon glycoside according to claim 5, characterized in that: The ligand is selected from one of the following structures: 。 9. A method for synthesizing a functionalized carbon glycoside according to claim 8, characterized in that: The ligand is 4,4′-di-tert-butyl-2,2′-bipyridine or 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine.

10. The method for synthesizing a functionalized carbon glycoside according to claim 1, characterized in that: The reaction temperature is 25°C and the reaction time is 48-60 h.

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