Carbohydrate Chemistry in the Total Synthesis of Naturally Occurring Glycosides

Revolutionize your manufacturing processes and more with this groundbreaking introduction

Carbohydrates and complex glycosides are important classes of molecules. The ubiquitous glycosides are extremely diverse in structure and functions, and many of them are of pharmacological significance. Purification of a homogeneous glycoside from the nature sources, especially in an appreciable amount, is always difficult. Chemical synthesis provides a feasible access to the homogenous glycosides and their congeners.

Carbohydrate Chemistry in the Total Synthesis of Naturally Occurring Glycosides presents about 10 families of naturally occurring glycoside natural products, including about 150 molecules that organic chemists have devoted a lot of effort toward their synthesis. In each example, the background of each natural glycoside, including its natural resources, its isolation process and its bioactivities have been described; the total synthesis of the natural glycoside is presented with special emphasis on the glycosylation reaction, the strategy on saccharides assembly, the protecting group manipulation, and the method for the synthesis of the rare saccharide units. Readers can clearly see the progress of total synthesis of naturally occurring glycosides, from early to current arts, from simple to complex molecules, and from tedious strategy to highly efficient and economical methodologies in this book. It will highly benefit the further developments in the total synthesis of naturally occurring glycosides and synthetic carbohydrate chemistry.

Carbohydrate Chemistry in the Total Synthesis of Naturally Occurring Glycosides is ideal for Organic Chemists, Biochemists, Pharmaceutical and Medicinal Chemists, Natural Products Chemists, and Pharmaceutical Industry

Preface xi

List of Abbreviations xiii

1 Introduction 1

References 5

2 Aromatic Polyketide Glycosides 7

Landomycin A 7

Olivomycin A 13

Ciclamycin 17

Vineomycin B2 20

Trioxacarcin 25

Daunorubicin 29

Aquayamycin 30

Vineomycin A1 30

Derhodinosylurdamycin A 31

Jadomycins 31

Tan-1085 33

Benanomicins and Pradimicins 33

Pluramycins 34

Marmycins 35

Cassialoin 36

FD-594 36

Calixanthomycin A 38

Lactonamycin 38

Lomaiviticin A(−) 39

References 42

3 Enediyne Glycosides 47

Calicheamicin γ_I¹ 48

Namenamicin 54

Shishijimicin A 56

Neocarzinostatin Chromophore 58

Maduropeptin Chromophore 59

References 61

4 Flavonoid Glycosides 63

Flavonol 3-O-glycosides 65

Quercetin 3-sophorotrioside 65

Sl0101 66

Flavone and Isoflavone 7-O-Glycosides 67

A-76202 67

Flavonol 3-O- and 7-O-Bisglycosides 70

Kaempferitrin 70

Flavonol 5-O-Glycosides 71

Camellianin B 71

Flavone 6-C-Glycosides 72

Chafurosides 72

Cyanidin 3-O-Glycosides 74

Cyanidin 3-O-β-D-glucoside 74

Other Examples 75

Quercetin 3-O-β-D-Glucuronide 75

Quercetin 3-O-(2 ′′-Galloyl)-α-L-arabinopyranoside 75

Isoquercitrin Coumarate 75

Kaempferol 3-O-(3 ′′,6′′-di-O-E-p-coumaroyl)-β-D-Glucopyranoside 76

Platanoside 76

Quercetin-3-O-trisaccharide 79 78

Houttuynoid A 78

Daidzin, Genistin, Ononin, and Sissotrin 78

Apigenin 7-O-Cellobioside 79

Suttellarin 80

Calabricoside A 80

Kaempferol-3-O-7-O-bisglycoside 88 81

Vicenines 81

Carambolaflavone A 83

Flavocommeline 83

Schaftoside 84

Pelargonidin 3-O-6′′-O-acetyl-β-D-glucopyranoside 85

Cyanidin 4′-O-methyl-3-O-glucoside 86

References 86

5 Macrolide Glycosides 89

Erythromycin 89

Apoptolidin A 94

Spinosyn A (Lepicidin A) 98

Tiacumicin B 103

Pikromycin 106

Polycavernoside A 106

Auriside A 107

Lyngbyaloside B 108

Avermectin 109

Formamicin 109

Tylosin 109

Mangrolide 112

Amphotericin B 113

Aldgamycins 113

Mycinamicin IV 114

References 115

6 Nucleosides 119

Tunicamycin 119

Hikizimycin 126

Herbicidins 128

A201A 131

Amipurimycin 134

Caprazamycin 137

Polyoxin J 141

Octosyl Acid A 142

HF-7 143

Malayamycin 143

Capuramycin 144

Muraymycin 144

Plicacetin, Streptcytosine A, and Amicetin 145

A-94964 146

Miharamycin B 148

References 149

7 Peptide Glycosides 153

Vancomycin 155

Bleomycin A2 159

Mannopeptimycin 165

Syndecan 170

Lipoglycopeptide Arylomycin 171

References 172

8 Resin Glycosides 175

Calonyctin A 176

Tricolorin 179

Ipomoeassin 185

Woodrosin I 189

Batatosides l 191

Batatin VI 191

Merremoside d 192

Murucoidins 192

References 195

9 Steroid Glycosides 197

Cholestane Type Steroid Glycosides 197

OSW-1 197

Periploside A 201

Luzonicosides and Sepositoside 204

Cardenolide Type Steroid Glycosides 207

Digitoxin 207

Furostane Type Steroid Glycosides 212

Furostan Saponin and Methyl Protodioscin 212

Spirostan Type Steroid Glycosides 214

Desgalactotigonin 214

Forbeside E 216

Osladin 216

Pavonimin 218

Dioscin 218

Polyphyllin D 219

Maidong Saponin C 220

Xiebai Saponin I 221

Candicanoside A 222

Ouabain 222

Timosaponin BII 223

Solamargine 223

Rhodexins 225

Goniopectenoside B 226

Astrosterioside A 226

Linckoside 227

Trewianin 228

P57 228

Oleandrin 230

References 231

10 Triterpenoid Glycosides 233

Ciwujianoside C3 233

QS-21 234

Lobatoside E 238

Ginsenosides 239

Echinoside A 242

Anemoclemoside B 245

Betavugaroside III 247

Δ²⁰-Ginsenosides 247

Flaccidoside II 248

Asiaticoside 249

Pulsatilla Saponin D 249

Lotoidoside D 250

Astragalosides 252

Chikusetsu Saponins 253

References 253

11 Miscellaneous Glycosides 257

Allosamidin 257

Staurosporine 257

Everninomicin 13,384-1 259

Brasilicardins 263

Efrotomycin 266

Peyssonoside A 267

Amycolamicin/Kibdelomycin 268

Strictosidine-Type Indole Alkaloid Glycosides 268

Cotylenin A 270

Pyrolaside B 271

References 273

Index 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.