Biao Yu is Professor and currently Director of State Key Laboratory of Bioorganic and Natural Products Chemistry at Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences. He was given the Humboldt Research Award from the Alexander von Humboldt Foundation in 2020, the Roy L. Whistler Award from the International Carbohydrate Organization in 2022, and was elected as the Academician of the Chinese Academy of Sciences in 2021. He has spent nearly 30 years working on carbohydrate chemistry, especially the total synthesis of naturally occurring glycosides. Xiaoyu Yang is Associate Professor at the School of Physical Science and Technology, ShanghaiTech University, China. His research interests focus on organic synthesis, asymmetric catalysis, carbohydrate chemistry and chemical biology.

• Preface xiList of Abbreviations xiii1 Introduction 1References 52 Aromatic Polyketide Glycosides 7Landomycin A 7Olivomycin A 13Ciclamycin 17Vineomycin B2 20Trioxacarcin 25Daunorubicin 29Aquayamycin 30Vineomycin A1 30Derhodinosylurdamycin A 31Jadomycins 31Tan-1085 33Benanomicins and Pradimicins 33Pluramycins 34Marmycins 35Cassialoin 36FD-594 36Calixanthomycin A 38Lactonamycin 38Lomaiviticin A(−) 39References 423 Enediyne Glycosides 47Calicheamicin γI1 48Namenamicin 54Shishijimicin A 56Neocarzinostatin Chromophore 58Maduropeptin Chromophore 59References 614 Flavonoid Glycosides 63Flavonol 3-O-glycosides 65Quercetin 3-sophorotrioside 65Sl0101 66Flavone and Isoflavone 7-O-Glycosides 67A-76202 67Flavonol 3-O- and 7-O-Bisglycosides 70Kaempferitrin 70Flavonol 5-O-Glycosides 71Camellianin B 71Flavone 6-C-Glycosides 72Chafurosides 72Cyanidin 3-O-Glycosides 74Cyanidin 3-O-β-D-glucoside 74Other Examples 75Quercetin 3-O-β-D-Glucuronide 75Quercetin 3-O-(2 ′′-Galloyl)-α-L-arabinopyranoside 75Isoquercitrin Coumarate 75Kaempferol 3-O-(3 ′′,6′′-di-O-E-p-coumaroyl)-β-D-Glucopyranoside 76Platanoside 76Quercetin-3-O-trisaccharide 79 78Houttuynoid A 78Daidzin, Genistin, Ononin, and Sissotrin 78Apigenin 7-O-Cellobioside 79Suttellarin 80Calabricoside A 80Kaempferol-3-O-7-O-bisglycoside 88 81Vicenines 81Carambolaflavone A 83Flavocommeline 83Schaftoside 84Pelargonidin 3-O-6′′-O-acetyl-β-D-glucopyranoside 85Cyanidin 4′-O-methyl-3-O-glucoside 86References 865 Macrolide Glycosides 89Erythromycin 89Apoptolidin A 94Spinosyn A (Lepicidin A) 98Tiacumicin B 103Pikromycin 106Polycavernoside A 106Auriside A 107Lyngbyaloside B 108Avermectin 109Formamicin 109Tylosin 109Mangrolide 112Amphotericin B 113Aldgamycins 113Mycinamicin IV 114References 1156 Nucleosides 119Tunicamycin 119Hikizimycin 126Herbicidins 128A201A 131Amipurimycin 134Caprazamycin 137Polyoxin J 141Octosyl Acid A 142HF-7 143Malayamycin 143Capuramycin 144Muraymycin 144Plicacetin, Streptcytosine A, and Amicetin 145A-94964 146Miharamycin B 148References 1497 Peptide Glycosides 153Vancomycin 155Bleomycin A2 159Mannopeptimycin 165Syndecan 170Lipoglycopeptide Arylomycin 171References 1728 Resin Glycosides 175Calonyctin A 176Tricolorin 179Ipomoeassin 185Woodrosin I 189Batatosides l 191Batatin VI 191Merremoside d 192Murucoidins 192References 1959 Steroid Glycosides 197Cholestane Type Steroid Glycosides 197OSW-1 197Periploside A 201Luzonicosides and Sepositoside 204Cardenolide Type Steroid Glycosides 207Digitoxin 207Furostane Type Steroid Glycosides 212Furostan Saponin and Methyl Protodioscin 212Spirostan Type Steroid Glycosides 214Desgalactotigonin 214Forbeside E 216Osladin 216Pavonimin 218Dioscin 218Polyphyllin D 219Maidong Saponin C 220Xiebai Saponin I 221Candicanoside A 222Ouabain 222Timosaponin BII 223Solamargine 223Rhodexins 225Goniopectenoside B 226Astrosterioside A 226Linckoside 227Trewianin 228P57 228Oleandrin 230References 23110 Triterpenoid Glycosides 233Ciwujianoside C3 233QS-21 234Lobatoside E 238Ginsenosides 239Echinoside A 242Anemoclemoside B 245Betavugaroside III 247Δ20-Ginsenosides 247Flaccidoside II 248Asiaticoside 249Pulsatilla Saponin D 249Lotoidoside D 250Astragalosides 252Chikusetsu Saponins 253References 25311 Miscellaneous Glycosides 257Allosamidin 257Staurosporine 257Everninomicin 13,384-1 259Brasilicardins 263Efrotomycin 266Peyssonoside A 267Amycolamicin/Kibdelomycin 268Strictosidine-Type Indole Alkaloid Glycosides 268Cotylenin A 270Pyrolaside B 271References 273Index 275

Biao Yu is Professor and currently Director of State Key Laboratory of Bioorganic and Natural Products Chemistry at Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences. He was given the Humboldt Research Award from the Alexander von Humboldt Foundation in 2020, the Roy L. Whistler Award from the International Carbohydrate Organization in 2022, and was elected as the Academician of the Chinese Academy of Sciences in 2021. He has spent nearly 30 years working on carbohydrate chemistry, especially the total synthesis of naturally occurring glycosides. Xiaoyu Yang is Associate Professor at the School of Physical Science and Technology, ShanghaiTech University, China. His research interests focus on organic synthesis, asymmetric catalysis, carbohydrate chemistry and chemical biology.

• Preface xiList of Abbreviations xiii1 Introduction 1References 52 Aromatic Polyketide Glycosides 7Landomycin A 7Olivomycin A 13Ciclamycin 17Vineomycin B2 20Trioxacarcin 25Daunorubicin 29Aquayamycin 30Vineomycin A1 30Derhodinosylurdamycin A 31Jadomycins 31Tan-1085 33Benanomicins and Pradimicins 33Pluramycins 34Marmycins 35Cassialoin 36FD-594 36Calixanthomycin A 38Lactonamycin 38Lomaiviticin A(−) 39References 423 Enediyne Glycosides 47Calicheamicin γI1 48Namenamicin 54Shishijimicin A 56Neocarzinostatin Chromophore 58Maduropeptin Chromophore 59References 614 Flavonoid Glycosides 63Flavonol 3-O-glycosides 65Quercetin 3-sophorotrioside 65Sl0101 66Flavone and Isoflavone 7-O-Glycosides 67A-76202 67Flavonol 3-O- and 7-O-Bisglycosides 70Kaempferitrin 70Flavonol 5-O-Glycosides 71Camellianin B 71Flavone 6-C-Glycosides 72Chafurosides 72Cyanidin 3-O-Glycosides 74Cyanidin 3-O-β-D-glucoside 74Other Examples 75Quercetin 3-O-β-D-Glucuronide 75Quercetin 3-O-(2 ′′-Galloyl)-α-L-arabinopyranoside 75Isoquercitrin Coumarate 75Kaempferol 3-O-(3 ′′,6′′-di-O-E-p-coumaroyl)-β-D-Glucopyranoside 76Platanoside 76Quercetin-3-O-trisaccharide 79 78Houttuynoid A 78Daidzin, Genistin, Ononin, and Sissotrin 78Apigenin 7-O-Cellobioside 79Suttellarin 80Calabricoside A 80Kaempferol-3-O-7-O-bisglycoside 88 81Vicenines 81Carambolaflavone A 83Flavocommeline 83Schaftoside 84Pelargonidin 3-O-6′′-O-acetyl-β-D-glucopyranoside 85Cyanidin 4′-O-methyl-3-O-glucoside 86References 865 Macrolide Glycosides 89Erythromycin 89Apoptolidin A 94Spinosyn A (Lepicidin A) 98Tiacumicin B 103Pikromycin 106Polycavernoside A 106Auriside A 107Lyngbyaloside B 108Avermectin 109Formamicin 109Tylosin 109Mangrolide 112Amphotericin B 113Aldgamycins 113Mycinamicin IV 114References 1156 Nucleosides 119Tunicamycin 119Hikizimycin 126Herbicidins 128A201A 131Amipurimycin 134Caprazamycin 137Polyoxin J 141Octosyl Acid A 142HF-7 143Malayamycin 143Capuramycin 144Muraymycin 144Plicacetin, Streptcytosine A, and Amicetin 145A-94964 146Miharamycin B 148References 1497 Peptide Glycosides 153Vancomycin 155Bleomycin A2 159Mannopeptimycin 165Syndecan 170Lipoglycopeptide Arylomycin 171References 1728 Resin Glycosides 175Calonyctin A 176Tricolorin 179Ipomoeassin 185Woodrosin I 189Batatosides l 191Batatin VI 191Merremoside d 192Murucoidins 192References 1959 Steroid Glycosides 197Cholestane Type Steroid Glycosides 197OSW-1 197Periploside A 201Luzonicosides and Sepositoside 204Cardenolide Type Steroid Glycosides 207Digitoxin 207Furostane Type Steroid Glycosides 212Furostan Saponin and Methyl Protodioscin 212Spirostan Type Steroid Glycosides 214Desgalactotigonin 214Forbeside E 216Osladin 216Pavonimin 218Dioscin 218Polyphyllin D 219Maidong Saponin C 220Xiebai Saponin I 221Candicanoside A 222Ouabain 222Timosaponin BII 223Solamargine 223Rhodexins 225Goniopectenoside B 226Astrosterioside A 226Linckoside 227Trewianin 228P57 228Oleandrin 230References 23110 Triterpenoid Glycosides 233Ciwujianoside C3 233QS-21 234Lobatoside E 238Ginsenosides 239Echinoside A 242Anemoclemoside B 245Betavugaroside III 247Δ20-Ginsenosides 247Flaccidoside II 248Asiaticoside 249Pulsatilla Saponin D 249Lotoidoside D 250Astragalosides 252Chikusetsu Saponins 253References 25311 Miscellaneous Glycosides 257Allosamidin 257Staurosporine 257Everninomicin 13,384-1 259Brasilicardins 263Efrotomycin 266Peyssonoside A 267Amycolamicin/Kibdelomycin 268Strictosidine-Type Indole Alkaloid Glycosides 268Cotylenin A 270Pyrolaside B 271References 273Index 275

Biao Yu is Professor and currently Director of State Key Laboratory of Bioorganic and Natural Products Chemistry at Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences. He was given the Humboldt Research Award from the Alexander von Humboldt Foundation in 2020, the Roy L. Whistler Award from the International Carbohydrate Organization in 2022, and was elected as the Academician of the Chinese Academy of Sciences in 2021. He has spent nearly 30 years working on carbohydrate chemistry, especially the total synthesis of naturally occurring glycosides. Xiaoyu Yang is Associate Professor at the School of Physical Science and Technology, ShanghaiTech University, China. His research interests focus on organic synthesis, asymmetric catalysis, carbohydrate chemistry and chemical biology.

• Preface xiList of Abbreviations xiii1 Introduction 1References 52 Aromatic Polyketide Glycosides 7Landomycin A 7Olivomycin A 13Ciclamycin 17Vineomycin B2 20Trioxacarcin 25Daunorubicin 29Aquayamycin 30Vineomycin A1 30Derhodinosylurdamycin A 31Jadomycins 31Tan-1085 33Benanomicins and Pradimicins 33Pluramycins 34Marmycins 35Cassialoin 36FD-594 36Calixanthomycin A 38Lactonamycin 38Lomaiviticin A(−) 39References 423 Enediyne Glycosides 47Calicheamicin γI1 48Namenamicin 54Shishijimicin A 56Neocarzinostatin Chromophore 58Maduropeptin Chromophore 59References 614 Flavonoid Glycosides 63Flavonol 3-O-glycosides 65Quercetin 3-sophorotrioside 65Sl0101 66Flavone and Isoflavone 7-O-Glycosides 67A-76202 67Flavonol 3-O- and 7-O-Bisglycosides 70Kaempferitrin 70Flavonol 5-O-Glycosides 71Camellianin B 71Flavone 6-C-Glycosides 72Chafurosides 72Cyanidin 3-O-Glycosides 74Cyanidin 3-O-β-D-glucoside 74Other Examples 75Quercetin 3-O-β-D-Glucuronide 75Quercetin 3-O-(2 ′′-Galloyl)-α-L-arabinopyranoside 75Isoquercitrin Coumarate 75Kaempferol 3-O-(3 ′′,6′′-di-O-E-p-coumaroyl)-β-D-Glucopyranoside 76Platanoside 76Quercetin-3-O-trisaccharide 79 78Houttuynoid A 78Daidzin, Genistin, Ononin, and Sissotrin 78Apigenin 7-O-Cellobioside 79Suttellarin 80Calabricoside A 80Kaempferol-3-O-7-O-bisglycoside 88 81Vicenines 81Carambolaflavone A 83Flavocommeline 83Schaftoside 84Pelargonidin 3-O-6′′-O-acetyl-β-D-glucopyranoside 85Cyanidin 4′-O-methyl-3-O-glucoside 86References 865 Macrolide Glycosides 89Erythromycin 89Apoptolidin A 94Spinosyn A (Lepicidin A) 98Tiacumicin B 103Pikromycin 106Polycavernoside A 106Auriside A 107Lyngbyaloside B 108Avermectin 109Formamicin 109Tylosin 109Mangrolide 112Amphotericin B 113Aldgamycins 113Mycinamicin IV 114References 1156 Nucleosides 119Tunicamycin 119Hikizimycin 126Herbicidins 128A201A 131Amipurimycin 134Caprazamycin 137Polyoxin J 141Octosyl Acid A 142HF-7 143Malayamycin 143Capuramycin 144Muraymycin 144Plicacetin, Streptcytosine A, and Amicetin 145A-94964 146Miharamycin B 148References 1497 Peptide Glycosides 153Vancomycin 155Bleomycin A2 159Mannopeptimycin 165Syndecan 170Lipoglycopeptide Arylomycin 171References 1728 Resin Glycosides 175Calonyctin A 176Tricolorin 179Ipomoeassin 185Woodrosin I 189Batatosides l 191Batatin VI 191Merremoside d 192Murucoidins 192References 1959 Steroid Glycosides 197Cholestane Type Steroid Glycosides 197OSW-1 197Periploside A 201Luzonicosides and Sepositoside 204Cardenolide Type Steroid Glycosides 207Digitoxin 207Furostane Type Steroid Glycosides 212Furostan Saponin and Methyl Protodioscin 212Spirostan Type Steroid Glycosides 214Desgalactotigonin 214Forbeside E 216Osladin 216Pavonimin 218Dioscin 218Polyphyllin D 219Maidong Saponin C 220Xiebai Saponin I 221Candicanoside A 222Ouabain 222Timosaponin BII 223Solamargine 223Rhodexins 225Goniopectenoside B 226Astrosterioside A 226Linckoside 227Trewianin 228P57 228Oleandrin 230References 23110 Triterpenoid Glycosides 233Ciwujianoside C3 233QS-21 234Lobatoside E 238Ginsenosides 239Echinoside A 242Anemoclemoside B 245Betavugaroside III 247Δ20-Ginsenosides 247Flaccidoside II 248Asiaticoside 249Pulsatilla Saponin D 249Lotoidoside D 250Astragalosides 252Chikusetsu Saponins 253References 25311 Miscellaneous Glycosides 257Allosamidin 257Staurosporine 257Everninomicin 13,384-1 259Brasilicardins 263Efrotomycin 266Peyssonoside A 267Amycolamicin/Kibdelomycin 268Strictosidine-Type Indole Alkaloid Glycosides 268Cotylenin A 270Pyrolaside B 271References 273Index 275