From Biosynthesis to Total Synthesis: Strategies and Tactics for Natural Products [Zografos - Wiley - Blackwell]
- ISBN/EAN
- 9781118751732
- Editore
- Wiley - Blackwell
- Formato
- Cartonato
- Anno
- 2016
- Pagine
- 584
Disponibile
175,50 €
Focusing on biosynthesis, this book provides readers with approaches and methodologies for modern organic synthesis. By discussing major biosynthetic pathways and their chemical reactions, transformations, and natural products applications; it links biosynthetic mechanisms and more efficient total synthesis.
• Describes four major biosynthetic pathways (acetate, mevalonate, shikimic acid, and mixed pathways and alkaloids) and their related mechanisms
• Covers reactions, tactics, and strategies for chemical transformations, linking biosynthetic processes and total synthesis
• Includes strategies for optimal synthetic plans and introduces a modern molecular approach to natural product synthesis and applications
• Acts as a key reference for industry and academic readers looking to advance knowledge in classical total synthesis, organic synthesis, and future directions in the field
Maggiori Informazioni
| Autore | Zografos Alexandros L. |
|---|---|
| Editore | Wiley - Blackwell |
| Anno | 2016 |
| Tipologia | Libro |
| Lingua | Inglese |
| Indice | 1 From Biosyntheses to Total Syntheses: An Introduction 1 Bastien Nay and Xu‐Wen Li 1.1 From Primary to Secondary Metabolism: the Key Building Blocks 1 1.1.1 Definitions 1 1.1.2 Energy Supply and Carbon Storing at the Early Stage of Metabolisms 1 1.1.3 Glucose as a Starting Material Toward Key Building Blocks of the Secondary Metabolism 1 1.1.4 Reactions Involved in the Construction of Secondary Metabolites 3 1.1.5 Secondary Metabolisms 4 1.2 From Biosynthesis to Total Synthesis: Strategies Toward the Natural Product Chemical Space 10 1.2.1 The Chemical Space of Natural Products 10 1.2.2 The Biosynthetic Pathways as an Inspiration for Synthetic Challenges 11 1.2.3 The Science of Total Synthesis 14 1.2.4 Conclusion: a Journey in the Future of Total Synthesis 16 References 16 SECTION I ACETATE BIOSYNTHETIC PATHWAY 19 2 Polyketides 21 Françoise Schaefers, Tobias A. M. Gulder, Cyril Bressy, Michael Smietana, Erica Benedetti, Stellios Arseniyadis, Markus Kalesse, and Martin Cordes 2.1 Polyketide Biosynthesis 21 2.1.1 Introduction 21 2.1.2 Assembly of Acetate/Malonate‐Derived Metabolites 23 2.1.3 Classification of Polyketide Biosynthetic Machineries 23 2.1.4 Conclusion 39 References 40 2.2 Synthesis of Polyketides 44 2.2.1 Asymmetric Alkylation Reactions 44 2.2.2 Applications of Asymmetric Alkylation Reactions in Total Synthesis of Polyketides and Macrolides 60 References 83 2.3 Synthesis of Polyketides‐Focus on Macrolides 87 2.3.1 Introduction 87 2.3.2 Stereoselective Synthesis of 1,3‐Diols: Asymmetric Aldol Reactions 88 2.3.3 Stereoselective Synthesis of 1,3‐Diols: Asymmetric Reductions 106 2.3.4 Application of Stereoselective Synthesis of 1,3‐Diols in the Total Synthesis of Macrolides 117 2.3.5 Conclusion 126 References 126 3 Fatty Acids and their Derivatives 130 Anders Vik and Trond Vidar Hansen 3.1 Introduction 130 3.2 Biosynthesis 130 3.2.1 Fatty Acids and Lipids 130 3.2.2 Polyunsaturated Fatty Acids 134 3.2.3 Mediated Oxidations of ω‐3 and ω‐6 Polyunsaturated Fatty Acids 135 3.3 Synthesis of ω‐3 and ω‐6 All‐Z Polyunsaturated Fatty Acids 140 3.3.1 Synthesis of Polyunsaturated Fatty Acids by the Wittig Reaction or by the Polyyne Semihydrogenation 140 3.3.2 Synthesis of Polyunsaturated Fatty Acids via Cross Coupling Reactions 143 3.4 A pplications in Total Synthesis of Polyunsaturated Fatty Acids 145 3.4.1 Palladium‐Catalyzed Cross Coupling Reactions 145 3.4.2 Biomimetic Transformations of Polyunsaturated Fatty Acids 149 3.4.3 Landmark Total Syntheses 153 3.4.4 Synthesis of Leukotriene B5 158 3.5 Conclusion 160 Acknowledgments 160 References 160 4 Polyethers 162 Youwei Xie and Paul E. Floreancig 4.1 Introduction 162 4.2 Biosynthesis 162 4.2.1 Ionophore Antibiotics 162 4.2.2 Marine Ladder Toxins 165 4.2.3 A nnonaceous Acetogenins and Terpene Polyethers 165 4.3 Epoxide Reactivity and Stereoselective Synthesis 166 4.3.1 Regiocontrol in Epoxide‐Opening Reactions 166 4.3.2 Stereoselective Epoxide Synthesis 172 4.4 A pplications to Total Synthesis 176 4.4.1 Acid‐Mediated Transformations 176 4.4.2 Cascades via Epoxonium Ion Formation 179 4.4.3 Cyclizations under Basic Conditions 181 4.4.4 Cyclization in Water 182 4.5 Conclusions 183 References 184 SECTION II MEVALONATE BIOSYNTHETIC PATHWAY 187 5 From Acetate to Mevalonate and Deoxyxylulose Phosphate Biosynthetic Pathways: an Introduction to Terpenoids 189 Alexandros L. Zografos and Elissavet E. Anagnostaki 5.1 Introduction 189 5.2 Mevalonic Acid Pathway 191 5.3 Mevalonate‐Independent Pathway 192 5.4 Conclusion 194 References 194 6 Monoterpenes and Iridoids 196 Mario Waser and Uwe Rinner 6.1 Introduction 196 6.2 Biosynthesis 196 6.2.1 A cyclic Monoterpenes 197 6.2.2 Cyclic Monoterpenes 197 6.2.3 Iridoids 200 6.2.4 Irregular Monoterpenes 202 6.3 A symmetric Organocatalysis 203 6.3.1 Introduction and Historical Background 204 6.3.2 Enamine, Iminium, and Singly Occupied Molecular Orbital Activation 207 6.3.3 Chiral (Bronsted) Acids and H‐Bonding Donors 213 6.3.4 Chiral Bronsted/Lewis Bases and Nucleophilic Catalysis 218 6.3.5 A symmetric Phase‐Transfer Catalysis 220 6.4 O rganocatalysis in the Total Synthesis of Iridoids and Monoterpenoid Indole Alkaloids 225 6.4.1 (+)‐Geniposide and 7‐Deoxyloganin 226 6.4.2 (–)‐Brasoside and (–)‐Littoralisone 227 6.4.3 (+)‐Mitsugashiwalactone 229 6.4.4 A lstoscholarine 229 6.4.5 (+)‐Aspidospermidine and (+)‐Vincadifformine 230 6.4.6 (+)‐Yohimbine 230 6.5 Conclusion 231 References 231 7 Sesquiterpenes 236 Alexandros L. Zografos and Elissavet E. Anagnostaki 7.1 Biosynthesis 236 7.2 Cycloisomerization Reactions in Organic Synthesis 244 7.2.1 Enyne Cycloisomerization 245 7.2.2 Diene Cycloisomerization 257 7.3 Application of Cycloisomerizations in the Total Synthesis of Sesquiterpenoids 266 7.3.1 Picrotoxane Sesquiterpenes 266 7.3.2 A romadendrane Sesquiterpenes: Epiglobulol 267 7.3.3 Cubebol–Cubebenes Sesquiterpenes 267 7.3.4 Ventricos‐7(13)‐ene 270 7.3.5 Englerins 271 7.3.6 Echinopines 271 7.3.7 Cyperolone 273 7.3.8 Diverse Sesquiterpenoids 276 7.4 Conclusion 276 References 276 8 Diterpenes 279 Louis Barriault 8.1 Introduction 279 8.2 Biosynthesis of Diterpenes Based on Cationic Cyclizations 1,2‐Shifts, and Transannular Processes 279 8.3 Pericyclic Reactions and their Application in the Synthesis of Selected Diterpenoids 284 8.3.1 Diels–Alder Reaction and Its Application in the Total Synthesis of Diterpenes 284 8.3.2 Cascade Pericyclic Reactions and their Application in the Total Synthesis of Diterpenes 291 8.4 Conclusion 293 References 294 9 Higher Terpenes and Steroids 296 Kazuaki Ishihara 9.1 Introduction 296 9.2 Biosynthesis 296 9.3 Cascade Polyene Cyclizations 303 9.3.1 Diastereoselective Polyene Cyclizations 303 9.3.2 “Chiral proton (H+)”‐Induced Polyene Cyclizations 304 9.3.3 “Chiral Metal Ion”‐Induced Polyene Cyclizations 308 9.3.4 “Chiral Halonium Ion (X+)”‐Induced Polyene Cyclizations 313 9.3.5 “Chiral Carbocation”‐Induced Polyene Cyclizations 319 9.3.6 Stereoselective Cyclizations of Homo(polyprenyl)arene Analogs 319 9.4 Biomimetic Total Synthesis of Terpenes and Steroids through Polyene Cyclization 319 9.5 Conclusion 328 References 328 SECTION III SHIKIMIC ACID BIOSYNTHETIC PATHWAY 331 10 Lignans, Lignins, and Resveratrols 333 Yu Peng 10.1 Biosynthesis 333 10.1.1 Primary Metabolism of Shikimic Acid and Aromatic Amino Acids 333 10.1.2 Lignans and Lignin 335 10.2 Auxiliary‐Assisted C(sp3)–H Arylation Reactions in Organic Synthesis 336 10.3 Friedel–Crafts Reactions in Organic Synthesis 344 10.4 Total Synthesis of Lignans by C(sp3)─H Arylation Reactions 353 10.5 Total Synthesis of Lignans and Polymeric Resveratrol by Friedel–Crafts Reactions 357 10.6 Conclusion 375 References 376 SECTION IV MIXED BIOSYNTHETIC PATHWAYS–THE STORY OF ALKALOIDS 381 11 Ornithine and Lysine Alkaloids 383 Sebastian Brauch, Wouter S. Veldmate, and Floris P. J. T. Rutjes 11.1 Biosynthesis of l‐Ornithine and l‐Lysine Alkaloids 383 11.1.1 Biosynthetic Formation of Alkaloids Derived from l‐Ornithine 383 11.1.2 Biosynthetic Formation of Alkaloids Derived from l‐Lysine 388 11.2 The Asymmetric Mannich Reaction in Organic Synthesis 392 11.2.1 Chiral Amines as Catalysts in Asymmetric Mannich Reactions 394 11.2.2 Chiral Bronsted Bases as Catalysts in Asymmetric Mannich Reactions 398 11.2.3 Chiral Bronsted Acids as Catalysts in Asymmetric Mannich Reactions 404 11.2.4 Organometallic Catalysts in Asymmetric Mannich Reactions 408 11.2.5 Biocatalytic Asymmetric Mannich Reactions 413 11.3 Mannich and Related Reactions in the Total Synthesis of l‐Lysine‐ and l‐Ornithine‐Derived Alkaloids 414 11.4 Conclusion 426 References 427 12 Tyrosine Alkaloids 431 Uwe Rinner and Mario Waser 12.1 Introduction 431 12.2 Biosynthesis of Tyrosine‐Derived Alkaloids 431 12.2.1 Phenylethylamines 431 12.2.2 Simple Tetrahydroisoquinoline Alkaloids 433 12.2.3 Modified Benzyltetrahydroisoquinoline Alkaloids 433 12.2.4 Phenethylisoquinoline Alkaloids 436 12.2.5 Amaryllidaceae Alkaloids 438 12.2.6 Biosynthetic Overview of Tyrosine‐Derived Alkaloids 442 12.3 Aryl–Aryl Coupling Reactions 442 12.3.1 Copper‐Mediated Aryl–Aryl Bond Forming Reactions 443 12.3.2 Nickel‐Mediated Aryl–Aryl Bond Forming Reactions 446 12.3.3 Palladium‐Mediated Aryl–Aryl Bond Forming Reactions 447 12.3.4 Transition Metal‐Catalyzed Couplings of Nonactivated Aryl Compounds 450 12.4 Synthesis of Tyrosine‐Derived Alkaloids 456 12.4.1 Synthesis of Modified Benzyltetrahydroisoquinoline Alkaloids 456 12.4.2 Synthesis of Phenethylisoquinoline Alkaloids 460 12.4.3 Synthesis of Amaryllidaceae Alkaloids 462 12.5 Conclusion 468 References 469 13 Histidine and Histidine‐Like Alkaloids 473 Ian S. Young 13.1 Introduction 473 13.2 Biosynthesis 473 13.3 Atom Economy and Protecting‐Group‐Free Chemistry 480 13.4 Challenging the Boundaries of Synthesis: Pias 488 13.5 Conclusion 497 References 499 14 Anthranilic Acid–Tryptophan Alkaloids 502 Zhen‐Yu Tang 14.1 Biosynthesis 502 14.2 Divergent Synthesis–Collective Total Synthesis 508 14.3 Collective Total Synthesis of Tryptophan‐Derived Alkaloids 510 14.3.1 Monoterpene Indole Alkaloids 510 14.3.2 Bisindole Alkaloids 512 References 517 15 Future Directions of Modern Organic Synthesis 519 Jakob Pletz and Rolf Breinbauer 15.1 Introduction 519 15.2 Enzymes in Organic Synthesis: Merging Total Synthesis with Biosynthesis 520 15.3 Engineered Biosynthesis 526 15.4 Diversity‐Oriented Synthesis, Biology‐Oriented Synthesis, and Diverted Total Synthesis 533 15.4.1 Diversity‐oriented Synthesis 535 15.4.2 Biology‐oriented Synthesis 536 15.4.3 Diverted Total Synthesis 539 15.5 Conclusion 541 References 545 INDEX 548 |
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