From biosynthesis to total synthesis : strategies and tactics for natural products / edited by Alexandros L. Zografos, Aristotle University of Thessaloniki, Greece.

Format:

Book

Contributor:

Zografos, Alexandros L., editor.

Language:

English

Subjects (All):

Organic compounds--Synthesis.

Organic compounds.

Biosynthesis.

Physical Description:

1 online resource (588 pages) : illustrations (some color)

Edition:

1st ed.

Place of Publication:

Hoboken, New Jersey : John Wiley & Sons, Incorporated, [2016]

Language Note:

English

Summary:

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

Contents:

Intro

Title Page

Copyright Page

Contents

List of Contributors

Preface

Chapter 1 From Biosyntheses to Total Syntheses: An Introduction

1.1 FROM PRIMARY TO SECONDARY METABOLISM: THE KEY BUILDING BLOCKS

1.1.1 Definitions

1.1.2 Energy Supply and Carbon Storing at the Early Stage of Metabolisms

1.1.3 Glucose as a Starting Material Toward Key Building Blocks of the Secondary Metabolism

1.1.4 Reactions Involved in the Construction of Secondary Metabolites

1.1.5 Secondary Metabolisms

1.2 FROM BIOSYNTHESIS TO TOTAL SYNTHESIS: STRATEGIES TOWARD THE NATURAL PRODUCT CHEMICAL SPACE

1.2.1 The Chemical Space of Natural Products

1.2.2 The Biosynthetic Pathways as an Inspiration for Synthetic Challenges

1.2.3 The Science of Total Synthesis

1.2.4 Conclusion: A Journey in the Future of Total Synthesis

REFERENCES

SECTION I ACETATE BIOSYNTHETIC PATHWAY

Chapter 2 Polyketides

2.1 POLYKETIDE BIOSYNTHESIS

2.1.1 Introduction

2.1.2 Assembly of Acetate/Malonate-Derived Metabolites

2.1.3 Classification of Polyketide Biosynthetic Machineries

2.1.4 Conclusion

References

2.2 SYNTHESIS OF POLYKETIDES

2.2.1 Asymmetric Alkylation Reactions

2.2.2 Applications of Asymmetric Alkylation Reactions in Total Synthesis of Polyketides and Macrolides

2.3 SYNTHESIS OF POLYKETIDES-FOCUS ON MACROLIDES

2.3.1 Introduction

2.3.2 Stereoselective Synthesis of 1,3-Diols: Asymmetric Aldol Reactions

2.3.3 Stereoselective Synthesis of 1,3-Diols: Asymmetric Reductions

2.3.4 Application of Stereoselective Synthesis of 1,3-Diols in the Total Synthesis of Macrolides

2.3.5 Conclusion

Chapter 3 FATTY ACIDS AND THEIR DERIVATIVES

3.1 INTRODUCTION

3.2 BIOSYNTHESIS

3.2.1 Fatty Acids and Lipids

3.2.2 Polyunsaturated Fatty Acids.

3.2.3 Mediated Oxidations of ω-3 and ω-6 Polyunsaturated Fatty Acids

3.3 SYNTHESIS OF ω-3 AND ω-6 ALL-Z POLYUNSATURATED FATTY ACIDS

3.3.1 Synthesis of Polyunsaturated Fatty Acids by the Wittig Reaction or by the Polyyne Semihydrogenation

3.3.2 Synthesis of Polyunsaturated Fatty Acids via Cross Coupling Reactions

3.4 APPLICATIONS IN TOTAL SYNTHESIS OF POLYUNSATURATED FATTY ACIDS

3.4.1 Palladium-Catalyzed Cross Coupling Reactions

3.4.2 Biomimetic Transformations of Polyunsaturated Fatty Acids

3.4.3 Landmark Total Syntheses

3.4.4 Synthesis of Leukotriene B5

3.5 CONCLUSION

ACKNOWLEDGMENTS

Chapter 4 Polyethers

4.1 INTRODUCTION

4.2 BIOSYNTHESIS

4.2.1 Ionophore Antibiotics

4.2.2 Marine Ladder Toxins

4.2.3 Annonaceous Acetogenins and Terpene Polyethers

4.3 EPOXIDE REACTIVITY AND STEREOSELECTIVE SYNTHESIS

4.3.1 Regiocontrol in Epoxide-Opening Reactions

4.3.2 Stereoselective Epoxide Synthesis

4.4 APPLICATIONS TO TOTAL SYNTHESIS

4.4.1 Acid-Mediated Transformations

4.4.2 Cascades via Epoxonium Ion Formation

4.4.3 Cyclizations under Basic Conditions

4.4.4 Cyclization in Water

4.5 CONCLUSIONS

SECTION II MEVALONATE BIOSYNTHETIC PATHWAY

Chapter 5 From Acetate to Mevalonate and Deoxyxylulose Phosphate Biosynthetic Pathways: An Introduction to Terpenoids

5.1 INTRODUCTION

5.2 MEVALONIC ACID PATHWAY

5.3 MEVALONATE-INDEPENDENT PATHWAY

5.4 CONCLUSION

Chapter 6 Monoterpenes and Iridoids

6.1 INTRODUCTION

6.2 BIOSYNTHESIS

6.2.1 Acyclic Monoterpenes

6.2.2 Cyclic Monoterpenes

6.2.3 Iridoids

6.2.4 Irregular Monoterpenes

6.3 ASYMMETRIC ORGANOCATALYSIS

6.3.1 Introduction and Historical Background

6.3.2 Enamine, Iminium, and Singly Occupied Molecular Orbital Activation.

6.3.3 Chiral (Brønsted) Acids and H-Bonding Donors

6.3.4 Chiral Brønsted/Lewis Bases and Nucleophilic Catalysis

6.3.5 Asymmetric Phase‐Transfer Catalysis

6.4 ORGANOCATALYSIS IN THE TOTAL SYNTHESIS OF IRIDOIDS AND MONOTERPENOID INDOLE ALKALOIDS

6.4.1 (+)-Geniposide and 7-Deoxyloganin

6.4.2 (-)-Brasoside and (-)-Littoralisone

6.4.3 (+)-Mitsugashiwalactone

6.4.4 Alstoscholarine

6.4.5 (+)-Aspidospermidine and (+)-Vincadifformine

6.4.6 (+)-Yohimbine

6.5 CONCLUSION

Chapter 7 Sesquiterpenes

7.1 BIOSYNTHESIS

7.2 CYCLOISOMERIZATION REACTIONS IN ORGANIC SYNTHESIS

7.2.1 Enyne Cycloisomerization

7.2.2 Diene Cycloisomerization

7.3 APPLICATION OF CYCLOISOMERIZATIONS IN THE TOTAL SYNTHESIS OF SESQUITERPENOIDS

7.3.1 Picrotoxane Sesquiterpenes

7.3.2 Aromadendrane Sesquiterpenes: Epiglobulol

7.3.3 Cubebol-Cubebenes Sesquiterpenes

7.3.4 Ventricos-7(13)-ene

7.3.5 Englerins

7.3.6 Echinopines

7.3.7 Cyperolone

7.3.8 Diverse Sesquiterpenoids

7.4 CONCLUSION

Chapter 8 Diterpenes

8.1 INTRODUCTION

8.2 BIOSYNTHESIS OF DITERPENES BASED ON CATIONIC CYCLIZATIONS, 1,2‐SHIFTS, AND TRANSANNULAR PROCESSES

8.3 PERICYCLIC REACTIONS AND THEIR APPLICATION IN THE SYNTHESIS OF SELECTED DITERPENOIDS

8.3.1 Diels-Alder Reaction and Its Application in the Total Synthesis of Diterpenes

8.3.2 Cascade Pericyclic Reactions and Their Application in the Total Synthesis of Diterpenes

8.4 CONCLUSION

Chapter 9 Higher Terpenes and Steroids

9.1 INTRODUCTION

9.2 BIOSYNTHESIS

9.3 CASCADE POLYENE CYCLIZATIONS

9.3.1 Diastereoselective Polyene Cyclizations

9.3.2 "Chiral proton (H+)"-Induced Polyene Cyclizations

9.3.3 "Chiral Metal Ion"-Induced Polyene Cyclizations

9.3.4 "Chiral Halonium Ion (X+)"-Induced Polyene Cyclizations.

9.3.5 "Chiral Carbocation"-Induced Polyene Cyclizations

9.3.6 Stereoselective Cyclizations of Homo(polyprenyl)arene Analogs

9.4 BIOMIMETIC TOTAL SYNTHESIS OF TERPENES AND STEROIDS THROUGH POLYENE CYCLIZATION

9.5 CONCLUSION

SECTION III SHIKIMIC ACID BIOSYNTHETIC PATHWAY

Chapter 10 Lignans, Lignins, and Resveratrols

10.1 BIOSYNTHESIS

10.1.1 Primary Metabolism of Shikimic Acid and Aromatic Amino Acids

10.1.2 Lignans and Lignin

10.2 AUXILIARY-ASSISTED C(sp3)-H ARYLATION REACTIONS IN ORGANIC SYNTHESIS

10.3 FRIEDEL-CRAFTS REACTIONS IN ORGANIC SYNTHESIS

10.4 TOTAL SYNTHESIS OF LIGNANS BY C(sp3)-H ARYLATION REACTIONS

10.5 TOTAL SYNTHESIS OF LIGNANS AND POLYMERIC RESVERATROL BY FRIEDEL-CRAFTS REACTIONS

10.6 CONCLUSION

SECTION IV MIXED BIOSYNTHETIC PATHWAYS-THE STORY OF ALKALOIDS

Chapter 11 Ornithine and Lysine Alkaloids

11.1 BIOSYNTHESIS OF l-ORNITHINE AND l-LYSINE ALKALOIDS

11.1.1 Biosynthetic Formation of Alkaloids Derived from l-Ornithine

11.1.2 Biosynthetic Formation of Alkaloids Derived from l-Lysine

11.2 THE ASYMMETRIC MANNICH REACTION IN ORGANIC SYNTHESIS

11.2.1 Chiral Amines as Catalysts in Asymmetric Mannich Reactions

11.2.2 Chiral Brønsted Bases as Catalysts in Asymmetric Mannich Reactions

11.2.3 Chiral Brønsted Acids as Catalysts in Asymmetric Mannich Reactions

11.2.4 Organometallic Catalysts in Asymmetric Mannich Reactions

11.2.5 Biocatalytic Asymmetric Mannich Reactions

11.3 MANNICH AND RELATED REACTIONS IN THE TOTAL SYNTHESIS OF l-LYSINE- AND l-ORNITHINE-DERIVED ALKALOIDS

11.4 CONCLUSION

Chapter 12 TYROSINE ALKALOIDS

12.1 INTRODUCTION

12.2 BIOSYNTHESIS OF TYROSINE-DERIVED ALKALOIDS

12.2.1 Phenylethylamines

12.2.2 Simple Tetrahydroisoquinoline Alkaloids

12.2.3 Modified Benzyltetrahydroisoquinoline Alkaloids.

12.2.4 Phenethylisoquinoline Alkaloids

12.2.5 Amaryllidaceae Alkaloids

12.2.6 Biosynthetic Overview of Tyrosine-Derived Alkaloids

12.3 ARYL-ARYL COUPLING REACTIONS

12.3.1 Copper-Mediated Aryl-Aryl Bond Forming Reactions

12.3.2 Nickel-Mediated Aryl-Aryl Bond Forming Reactions

12.3.3 Palladium-Mediated Aryl-Aryl Bond Forming Reactions

12.3.4 Transition Metal-Catalyzed Couplings of Nonactivated Aryl Compounds

12.4 SYNTHESIS OF TYROSINE-DERIVED ALKALOIDS

12.4.1 Synthesis of Modified Benzyltetrahydroisoquinoline Alkaloids

12.4.2 Synthesis of Phenethylisoquinoline Alkaloids

12.4.3 Synthesis of Amaryllidaceae Alkaloids

12.5 CONCLUSION

Chapter 13 Histidine and Histidine-Like Alkaloids

13.1 INTRODUCTION

13.2 BIOSYNTHESIS

13.3 ATOM ECONOMY AND PROTECTING-GROUP-FREE CHEMISTRY

13.4 CHALLENGING THE BOUNDARIES OF SYNTHESIS: PIAs

13.5 CONCLUSION

Chapter 14 Anthranilic Acid-Tryptophan Alkaloids

14.1 BIOSYNTHESIS

14.2 DIVERGENT SYNTHESIS-COLLECTIVE TOTAL SYNTHESIS

14.3 COLLECTIVE TOTAL SYNTHESIS OF TRYPTOPHAN‐DERIVED ALKALOIDS

14.3.1 Monoterpene Indole Alkaloids

14.3.2 Bisindole Alkaloids

Chapter 15 FUTURE DIRECTIONS OF MODERN ORGANIC SYNTHESIS

15.1 INTRODUCTION

15.2 ENZYMES IN ORGANIC SYNTHESIS: MERGING TOTAL SYNTHESIS WITH BIOSYNTHESIS

15.3 ENGINEERED BIOSYNTHESIS

15.4 DIVERSITY-ORIENTED SYNTHESIS, BIOLOGY-ORIENTED SYNTHESIS, AND DIVERTED TOTAL SYNTHESIS

15.4.1 Diversity-oriented Synthesis

15.4.2 Biology-oriented Synthesis

15.4.3 Diverted Total Synthesis

15.5 CONCLUSION

Index

Supplemental Images

EULA.

Notes:

Bibliographic Level Mode of Issuance: Monograph

Includes bibliographical references and index.

Description based on print version record.

ISBN:

9781118753637

1118753631

9781118753569

1118753569

OCLC:

930875600