Stereoselective Multiple Bond-Forming Transformations in Organic Synthesis E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 587

Veröffentlichungsjahr: 2015

Beschreibung

Combining the important research topic of multiple bond-forming transformations with green chemistry, this book helps chemists identify recent sustainable stereoselective synthetic sequences.

•    Combines the important research topic of multiple bond-forming transformations with green chemistry and sustainable development
•    Offers a valuable resource for preparing compounds with multiple stereogenic centers, an important field for synthetic chemists
•    Organizes chapters by molecular structure of final products, making for a handbook-style resource
•    Discusses applications of the synthesis of natural products and of drug intermediates
•    Brings together otherwise-scattered information about a number of key, efficient chemical reactions

Leseprobe

Table of Contents

Cover

Title Page

Copyright

List of Contributors

Foreword

PREFACE

1: DEFINITIONS AND CLASSIFICATIONS OF MBFTs

1.1 INTRODUCTION

1.2 DEFINITIONS

1.3 CONCLUSION AND OUTLOOK

REFERENCES

PART I: STEREOSELECTIVE SYNTHESIS OF HETEROCYCLES

2: FIVE-MEMBERED HETEROCYCLES

2.1 INTRODUCTION

2.2 MONOCYCLIC TARGETS

2.3 FUSED POLYCYCLIC TARGETS

2.4 BRIDGED POLYCYCLIC TARGETS

2.5 CONCLUSION AND OUTLOOK

REFERENCES

3: SIX-MEMBERED HETEROCYCLES

3.1 INTRODUCTION

3.2 MONOCYCLIC TARGETS

3.3 FUSED POLYCYCLIC TARGETS

3.4 BRIDGED POLYCYCLIC TARGETS

3.5 POLYCYCLIC SPIRO TARGETS

3.6 SUMMARY AND OUTLOOK

REFERENCES

4: OTHER HETEROCYCLES

4.1 INTRODUCTION

4.2 SYNTHESIS OF MEDIUM-SIZED MONOCYCLIC, FUSED AND BRIDGED POLYCYCLIC HETEROCYCLES

4.3 SUMMARY AND OUTLOOK

REFERENCES

PART II: STEREOSELECTIVE SYNTHESIS OF CARBOCYCLES

5: THREE- AND FOUR-MEMBERED CARBOCYCLES

5.1 INTRODUCTION

5.2 CYCLOPROPANE DERIVATIVES

5.3 CYCLOBUTANE DERIVATIVES

5.4 SUMMARY AND OUTLOOK

REFERENCES

6: FIVE-MEMBERED CARBOCYCLES

6.1 INTRODUCTION

6.2 MONOCYCLIC TARGETS

6.3 FUSED POLYCYCLIC TARGETS

6.4 BRIDGED POLYCYCLIC TARGETS

6.5 CONCLUSION AND OUTLOOK

REFERENCES

7: STEREOSELECTIVE SYNTHESIS OF SIX-MEMBERED CARBOCYCLES

7.1 INTRODUCTION

7.2 METAL-CATALYZED STEREOSELECTIVE MULTIPLE BOND-FORMING TRANSFORMATIONS

7.3 ENANTIOSELECTIVE ORGANOCATALYZED SYNTHESIS OF SIX-MEMBERED RINGS

7.4 STEREOSELECTIVE MULTIPLE BOND-FORMING RADICAL TRANSFORMATIONS

7.5 CONCLUSIONS

REFERENCES

8: SEVEN- AND EIGHT-MEMBERED CARBOCYCLES

8.1 INTRODUCTION

8.2 CYCLOHEPTENES

8.3 CYCLOHEPTADIENES

8.4 CYCLOHEPTATRIENES

8.5 CYCLOOCTENES

8.6 CYCLOOCTADIENES

8.7 CYCLOOCTATRIENES

8.8 CYCLOOCTATETRAENES

8.9 CONCLUDING REMARKS

REFERENCES

PART III: STEREOSELECTIVE SYNTHESIS OF SPIROCYCLIC COMPOUNDS

9: METAL-ASSISTED METHODOLOGIES

9.1 INTRODUCTION

9.2 QUATERNARY SPIROCENTER

9.3 α-HETEROATOM-SUBSTITUTED SPIROCENTER

9.4 α,α′-Diheteroatom-Substituted Spirocenter

9.5 CONCLUSION AND OUTLOOK

REFERENCES

10: ORGANOCATALYZED METHODOLOGIES

10.1 INTRODUCTION

10.2 ENANTIOSELECTIVE SYNTHESIS OF ALL-CARBON SPIROCENTERS

10.3 ENANTIOSELECTIVE SYNTHESIS SPIROCENTERS WITH AT LEAST ONE HETEROATOM

10.4 CONCLUSION AND OUTLOOK

REFERENCES

PART IV: STEREOSELECTIVE SYNTHESIS OF ACYCLIC COMPOUNDS

11: METAL-CATALYZED METHODOLOGIES

11.1 INTRODUCTION

11.2 ANION RELAY APPROACH

11.3 MANNICH REACTION

11.4 REACTIONS INVOLVING ISONITRILES

11.5 1,2-ADDITION-TYPE PROCESSES

11.6 MICHAEL-TYPE PROCESSES

11.7 SUMMARY AND OUTLOOK

REFERENCES

12: ORGANOCATALYZED METHODOLOGIES

12.1 INTRODUCTION

12.2 AMINOCATALYSIS

12.3

N

-HETEROCYCLIC CARBENE (NHC) ACTIVATION

12.4 H-BONDING ACTIVATION

12.5 PHASE-TRANSFER CATALYSIS

12.6 SUMMARY AND OUTLOOK

REFERENCES

PART V: MULTIPLE BOND-FORMING TRANSFORMATIONS: SYNTHETIC APPLICATIONS

13: MBFTs FOR THE TOTAL SYNTHESIS OF NATURAL PRODUCTS

13.1 INTRODUCTION

13.2 ANIONIC-INITIATED MBFTs

13.3 CATIONIC-INITIATED MBFTs

13.4 RADICAL-MEDIATED MBFTs

13.5 PERICYCLIC MBFTs

13.6 TRANSITION-METAL-CATALYZED MBFTs

13.7 SUMMARY AND OUTLOOK

REFERENCES

14: SYNTHESIS OF BIOLOGICALLY RELEVANT MOLECULES

14.1 INTRODUCTION

14.2 ORGANOCATALYZED MBFT FOR BRM

14.3 MULTICOMPONENT MBFT FOR BRM

14.4 PALLADIUM-CATALYZED MBFT For BRM

14.5 CONCLUSION AND OUTLOOK

REFERENCES

15: INDUSTRIAL APPLICATIONS OF MULTIPLE BOND-FORMING TRANSFORMATIONS (MBFTs)

15.1 INTRODUCTION

15.2 APPLICATIONS OF MBFTs

15.3 SUMMARY AND OUTLOOK

REFERENCES

INDEX

End User License Agreement

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Guide

Cover

Table of Contents

Begin Reading

List of Illustrations

Scheme 1.1

Scheme 1.2

Scheme 1.3

Scheme 1.4

Scheme 2.1

Scheme 2.2

Figure 2.1

Figure 2.2

Scheme 2.3

Scheme 2.4

Scheme 2.5

Scheme 2.6

Scheme 2.7

Scheme 2.8

Scheme 2.9

Scheme 2.10

Scheme 2.11

Scheme 2.12

Scheme 2.13

Scheme 2.14

Scheme 2.15

Scheme 2.16

Scheme 2.17

Scheme 2.18

Scheme 2.19

Scheme 2.20

Scheme 2.21

Scheme 2.22

Scheme 2.23

Scheme 2.24

Scheme 2.25

Scheme 2.26

Scheme 2.27

Scheme 2.28

Scheme 2.29

Scheme 2.30

Scheme 2.31

Scheme 2.32

Scheme 2.33

Scheme 2.34

Scheme 2.35

Scheme 2.36

Scheme 2.37

Scheme 2.38

Scheme 2.39

Scheme 2.40

Scheme 2.41

Scheme 2.42

Scheme 2.43

Scheme 2.44

Scheme 2.45

Scheme 2.46

Scheme 2.47

Scheme 2.48

Scheme 2.49

Scheme 2.50

Figure 3.1

Figure 3.2

Scheme 3.1

Scheme 3.2

Scheme 3.3

Scheme 3.4

Scheme 3.5

Scheme 3.6

Scheme 3.7

Figure 3.3

Scheme 3.8

Scheme 3.9

Scheme 3.10

Scheme 3.11

Scheme 3.12

Scheme 3.13

Scheme 3.14

Scheme 3.15

Scheme 3.16

Scheme 3.17

Scheme 3.18

Scheme 3.19

Scheme 3.20

Scheme 3.21

Figure Schemes 3.22

Figure 3.24

Scheme 3.23

Scheme 3.25

Scheme 3.26

Scheme 3.27

Scheme 3.28

Scheme 3.29

Scheme 3.30

Scheme 3.31

Scheme 3.32

Scheme 3.33

Scheme 3.34

Scheme 3.35

Scheme 3.36

Scheme 3.37

Scheme 3.38

Scheme 3.39

Scheme 3.40

Scheme 3.41

Scheme 3.42

Scheme 3.43

Scheme 3.44

Scheme 4.1

Scheme 4.2

Scheme 4.3

Scheme 4.4

Scheme 4.5

Scheme 4.6

Scheme 4.7

Scheme 4.8

Scheme 4.9

Scheme 4.10

Scheme 4.11

Scheme 4.12

Scheme 4.13

Scheme 4.14

Scheme 4.15

Scheme 4.16

Scheme 4.17

Scheme 4.18

Scheme 4.19

Scheme 4.20

Scheme 4.21

Scheme 4.22

Scheme 4.23

Scheme 4.24

Scheme 4.25

Scheme 4.26

Scheme 4.27

Scheme 4.28

Scheme 5.1

Scheme 5.2

Scheme 5.3

Scheme 5.4

Scheme 5.5

Scheme 5.6

Scheme 5.7

Scheme 5.8

Scheme 5.9

Scheme 5.10

Scheme 5.11

Scheme 5.12

Scheme 5.13

Scheme 5.14

Scheme 5.15

Scheme 5.16

Scheme 5.17

Scheme 5.18

Scheme 5.19

Scheme 5.20

Scheme 5.21

Scheme 5.22

Scheme 5.23

Scheme 5.24

Scheme 5.25

Scheme 5.26

Scheme 5.27

Scheme 5.28

Scheme 5.29

Scheme 5.30

Scheme 5.31

Scheme 5.32

Scheme 5.33

Scheme 5.34

Scheme 5.35

Scheme 5.36

Scheme 5.37

Scheme 5.38

Scheme 5.39

Scheme 5.40

Scheme 5.41

Scheme 5.42

Scheme 5.43

Scheme 5.44

Scheme 5.45

Scheme 5.46

Scheme 5.47

Scheme 5.48

Scheme 5.49

Scheme 5.50

Scheme 5.51

Scheme 5.52

Scheme 5.53

Scheme 5.54

Scheme 6.1

Scheme 6.2

Scheme 6.3

Scheme 6.4

Scheme 6.5

Scheme 6.6

Scheme 6.7

Scheme 6.8

Scheme 6.9

Scheme 6.10

Scheme 6.11

Scheme 6.12

Scheme 6.13

Scheme 6.14

Scheme 6.15

Scheme 6.16

Scheme 6.17

Scheme 6.18

Scheme 6.19

Scheme 6.20

Scheme 6.21

Scheme 6.22

Scheme 6.23

Scheme 6.24

Scheme 6.25

Scheme 6.26

Scheme 6.27

Scheme 6.28

Scheme 6.29

Scheme 6.30

Scheme 6.31

Scheme 6.32

Scheme 6.33

Scheme 6.34

Scheme 6.35

Scheme 6.36

Scheme 6.37

Scheme 6.38

Scheme 6.39

Scheme 6.40

Scheme 6.41

Scheme 6.42

Scheme 6.43

Scheme 6.44

Scheme 7.1

Scheme 7.2

Scheme 7.3

Scheme 7.4

Scheme 7.5

Scheme 7.6

Scheme 7.7

Scheme 7.8

Scheme 7.9

Scheme 7.10

Scheme 7.11

Scheme 7.12

Scheme 7.13

Scheme 7.14

Scheme 7.15

Scheme 7.16

Scheme 7.17

Scheme 7.18

Scheme 7.19

Scheme 7.20

Scheme 7.21

Scheme 7.22

Scheme 7.23

Scheme 7.24

Scheme 7.25

Scheme 7.26

Scheme 7.27

Scheme 7.28

Scheme 7.29

Scheme 7.30

Scheme 7.31

Scheme 7.32

Scheme 7.33

Scheme 7.34

Scheme 7.35

Scheme 7.36

Scheme 7.37

Scheme 7.38

Scheme 7.39

Scheme 7.40

Scheme 7.41

Scheme 8.1

Scheme 8.2

Scheme 8.3

Scheme 8.4

Scheme 8.5

Scheme 8.6

Scheme 8.7

Scheme 8.8

Scheme 8.9

Scheme 8.10

Scheme 8.11

Scheme 8.12

Scheme 8.13

Scheme 8.14

Scheme 8.15

Scheme 8.16

Scheme 8.17

Scheme 8.18

Scheme 8.19

Scheme 8.20

Scheme 8.21

Scheme 8.22

Scheme 8.23

Scheme 8.24

Scheme 8.25

Scheme 8.26

Scheme 8.27

Scheme 8.28

Scheme 8.29

Scheme 8.30

Scheme 8.31

Scheme 8.32

Scheme 8.33

Scheme 8.34

Scheme 8.35

Scheme 8.36

Scheme 8.37

Scheme 8.38

Scheme 8.39

Scheme 8.40

Scheme 8.41

Figure 9.1

Figure 9.2

Scheme 9.1

Scheme 9.2

Scheme 9.3

Scheme 9.4

Scheme 9.5

Scheme 9.6

Scheme 9.7

Scheme 9.8

Scheme 9.9

Scheme 9.10

Scheme 9.11

Scheme 9.12

Figure 9.3

Scheme 9.13

Scheme 9.14

Scheme 9.15

Scheme 9.16

Scheme 9.17

Scheme 9.18

Scheme 9.19

Scheme 9.20

Scheme 9.21

Scheme 9.22

Scheme 9.23

Figure 9.4

Scheme 9.24

Scheme 9.25

Scheme 9.26

Scheme 9.27

Scheme 9.28

Figure 10.1

Figure 10.2

Figure 10.3

Figure 10.4

Scheme 10.1

Scheme 10.2

Scheme 10.3

Scheme 10.4

Scheme 10.5

Scheme 10.6

Scheme 10.7

Scheme 10.8

Scheme 10.9

Scheme 10.10

Scheme 10.11

Scheme 10.12

Scheme 10.13

Scheme 10.14

Scheme 10.15

Figure 10.5

Scheme 10.16

Scheme 10.17

Scheme 10.18

Scheme 10.19

Scheme 10.20

Scheme 10.21

Scheme 10.22

Scheme 10.23

Scheme 10.24

Scheme 10.25

Scheme 10.26

Scheme 10.27

Scheme 10.28

Scheme 10.29

Scheme 10.30

Scheme 10.31

Scheme 10.32

Scheme 10.33

Scheme 10.34

Scheme 10.35

Scheme 10.36

Scheme 10.37

Scheme 10.38

Scheme 10.39

Scheme 10.40

Scheme 11.1

Scheme 11.2

Scheme 11.3

Scheme 11.4

Scheme 11.5

Scheme 11.6

Scheme 11.7

Scheme 11.8

Scheme 11.9

Scheme 11.10

Scheme 11.11

Scheme 11.12

Scheme 11.13

Scheme 11.14

Scheme 11.15

Scheme 11.16

Scheme 11.17

Scheme 11.18

Scheme 11.19

Scheme 11.20

Scheme 11.21

Scheme 11.22

Scheme 11.23

Scheme 11.24

Scheme 11.25

Scheme 11.26

Scheme 11.27

Scheme 11.28

Scheme 11.29

Scheme 11.30

Scheme 11.31

Scheme 12.1

Scheme 12.2

Scheme 12.3

Scheme 12.4

Scheme 12.5

Scheme 12.6

Scheme 12.7

Scheme 12.8

Scheme 12.9

Scheme 12.10

Scheme 12.11

Scheme 12.12

Scheme 12.13

Scheme 12.14

Scheme 12.15

Scheme 12.16

Scheme 12.17

Scheme 12.18

Scheme 12.19

Scheme 12.20

Scheme 12.21

Scheme 12.22

Figure 12.1

Scheme 12.23

Scheme 12.24

Scheme 12.25

Scheme 12.26

Scheme 12.27

Scheme 12.28

Scheme 12.29

Scheme 13.1

Scheme 13.2

Scheme 13.3

Scheme 13.4

Scheme 13.5

Scheme 13.6

Scheme 13.7

Scheme 13.8

Scheme 13.9

Scheme 13.10

Scheme 13.11

Scheme 13.12

Scheme 13.13

Scheme 13.14

Scheme 13.15

Scheme 13.16

Scheme 13.17

Scheme 13.18

Scheme 13.19

Scheme 13.20

Scheme 13.21

Scheme 13.22

Scheme 13.23

Scheme 13.24

Scheme 13.25

Scheme 13.26

Scheme 14.1

Scheme 14.2

Scheme 14.3

Scheme 14.4

Scheme 14.5

Scheme 14.6

Scheme 14.7

Scheme 14.8

Scheme 14.9

Scheme 14.10

Scheme 14.11

Scheme 14.12

Scheme 14.13

Scheme 14.14

Scheme 14.15

Scheme 14.16

Scheme 14.17

Scheme 14.18

Scheme 14.19

Scheme 14.20

Scheme 14.21

Scheme 14.22

Scheme 14.23

Scheme 14.24

Scheme 14.25

Scheme 15.1

Scheme 15.2

Figure 15.1

Scheme 15.3

Scheme 15.4

Scheme 15.5

Scheme 15.6

Scheme 15.7

Figure 15.2

Scheme 15.8

Scheme 15.9

Scheme 15.10

Scheme 15.11

Figure 15.3

Scheme 15.12

Scheme 15.13

Scheme 15.14

Scheme 15.15

Scheme 15.16

Scheme 15.17

Scheme 15.18

Scheme 15.19

Scheme 15.20

Scheme 15.21

Scheme 15.22

Figure 15.4

Scheme 15.23

Scheme 15.24

Scheme 15.25

Scheme 15.26

STEREOSELECTIVE MULTIPLE BOND-FORMING TRANSFORMATIONS IN ORGANIC SYNTHESIS

Edited byJEAN RODRIGUEZ AND DAMIEN BONNE

Copyright © 2015 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Stereoselective multiple bond-forming transformations in organic synthesis / edited by Jean Rodriguez, Damien Bonne.

pages cm

Includes bibliographical references and index.

ISBN 978-1-118-67271-6 (cloth)

1. Organic compounds–Synthesis. 2. Stereochemistry. 3. Chemical reactions. I. Rodriguez, Jean, editor. II. Bonne, Damien, 1979- editor.

QD262.S83 2015

547′.2–dc23

2014046406

Cover image courtesy of Jean Rodriguez and Damien Bonne.

List of Contributors

Muriel Amatore

, Sorbonne Universités, UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire (IPCM), Paris, France

Corinne Aubert

, Sorbonne Universités, UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire (IPCM), Paris, France

Marion Barbazanges

, Sorbonne Universités, UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire (IPCM), Paris, France

Damien Bonne

, Aix Marseille Université, CNRS, Marseille, France

Gérard Buono

, Aix Marseille Université, Centrale Marseille, CNRS, Marseille, France

Jean-Marc Campagne

, Institut Charles Gerhardt Montpellier, Ecole Nationale Supérieure de Chimie, France

Gaëlle Chouraqui

, Aix Marseille Université, Centrale Marseille, CNRS, Marseille, France

Hervé Clavier

, Aix Marseille Université, Centrale Marseille, CNRS, Marseille, France

Vincent Coeffard

, Institut Lavoisier de Versailles, Université de Versailles-St-Quentin-en-Yvelines, Versailles, France

Laurent Commeiras

, Aix Marseille Université, Centrale Marseille, CNRS, Marseille, France

Alexander Dömling

, Department of Drug Design, University of Groningen, Groningen, The Netherlands

Renata Marcia de Figueiredo

, Institut Charles Gerhardt Montpellier, Ecole Nationale Supérieure de Chimie, France

Laurent Giordano

, Aix Marseille Université, Centrale Marseille, CNRS, Marseille, France

Christine Greck

, Institut Lavoisier de Versailles, Université de Versailles-St-Quentin-en-Yvelines, Versailles, France

Gabriela Guillena

, Instituto de Síntesis Orgánica (ISO) and Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Alicante, Alicante, Spain

Hanmin Huang

, State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, China

Yanxing Jia

, Peking University Health Science Center, Beijing, China

Matthijs J

.

van Lint

, Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam, Amsterdam, The Netherlands

J. Carlos Menéndez

, Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense, Madrid, Spain

Xavier Moreau

, Institut Lavoisier de Versailles, Université de Versailles-St-Quentin-en-Yvelines, Versailles, France

Marine Desage-El Murr

, Sorbonne Universités, UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire (IPCM), Paris, France

Vijay Nair

, Organic Chemistry Section, National Institute of Interdisciplinary Science and Technology (NIIST), Kerala, India

Gilles Niel

, Institut Charles Gerhardt Montpellier, Ecole Nationale Supérieure de Chimie, France

Cyril Ollivier

, Sorbonne Universités, UPMC Univ Paris 06, Institut Parisien de Chimie Moléculaire (IPCM), Paris, France

Romano V.A. Orru

, Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam, Amsterdam, The Netherlands

Jean-Luc Parrain

, Aix Marseille Université, Centrale Marseille, CNRS, Marseille, France

Rony Rajan Paul

, Department of Chemistry, Christian College, Organic Chemistry Section, National Institute of Interdisciplinary Science and Technology (NIIST), Kerala, India

Diego J. Ramón

, Instituto de Síntesis Orgánica (ISO) and Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Alicante, Alicante, Spain

M. Teresa Ramos

, Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense, Madrid, Spain

Ramon Rios

, University of Southampton, UK

Jean Rodriguez

, Aix Marseille Université, CNRS, Marseille, France

Eelco Ruijter

, Department of Chemistry and Pharmaceutical Sciences, VU University Amsterdam, Amsterdam, The Netherlands

Alphonse Tenaglia

, Aix Marseille Université, Centrale Marseille, CNRS, Marseille, France

Giammarco Tenti

, Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense, Madrid, Spain

Christine Thomassigny

, Institut Lavoisier de Versailles, Université de Versailles-St-Quentin-en-Yvelines, Versailles, France

Qian Wang

, Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

Pan Xie

, State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, China

Ahmad Yazbak

, Synthatex Fine Chemicals Ltd, Israel

Tryfon Zarganes-Tzitzikas

, Department of Drug Design, University of Groningen, Groningen, The Netherlands

Jieping Zhu

, Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

Foreword

Dieter Enders

Institute of Organic Chemistry, RWTH Aachen, Aachen, Germany

It has always been the dream of chemists to imitate nature's enzyme catalyzed machinery in the chemo- and stereoselective synthesis of complex molecules under mild conditions in the compartment of a living cell. While nature has needed billions of years on our planet to reach such a level of elegance and synthetic efficiency, chemists have only had less than two hundred years to develop synthetic methodologies in the laboratory. In our science “to synthesize” basically means to form new chemical bonds, and it is, therefore, not surprising that at a rather early stage in history scientists tried to create several bonds by development of new one-pot multiple bond-forming transformations (MBFTs) involving one-, two-, and multicomponent conditions. Famous cases are the pioneer synthesis of amino acids reported by Adolph Strecker in 1850 or the more recent biomimetic polycyclization approach to steroids by Johnson. Other well-known one-pot MBFTs followed, for example, the Hantzsch dihydropyridine synthesis, later used in industry to synthesize the calcium antagonist Adalat®. However, it took quite a long time until Ivar Ugi reported his four-component reaction in the late 1950s, which became an eye-opener for the chemical community as a fundamental synthetic principle. One of its important industrial applications is the synthesis of the piperazine-amide core structure of the HIV protease inhibitor Crixivan®.

Confronted with the need to develop a sustainable chemistry, we have witnessed an amazing increase in the efficiency and selectivity of synthetic methods in the last fifty years. In order to solve the problems associated with the traditional step-by-step procedures, such as the cumbersome, time-consuming, and expensive isolation of intermediates, several new criteria have been introduced: atom, redox, step and pot economy or protecting-group-free synthesis. It is obvious that all variants of one-pot domino and cascade reactions or multicomponent consecutive reactions sequences may allow fulfilling these criteria.

Guided by nature, the asymmetric catalysis (metal catalysis, biocatalysis, and organocatalysis) is the method of choice when it comes to the chemo- and stereoselective synthesis of complex bioactive molecules bearing a number of stereocenters. Especially the rapid growth of the research area of organocatalysis since the turn of the millennium has enabled us to reach exceptionally high diastereo- and enantioselectivities under very mild catalytic conditions. When in 2006 our group developed a multicomponent organocatalytic triple domino reaction, I did not expect to see virtually complete asymmetric inductions in almost all the cases we tested. Nowadays, endowed with such powerful protocols and by employing the many technical extensions, such as solid phase and flow syntheses or combinatorial approaches, our synthesis arsenal offers many options for multiple bond-forming cascades.

The editors Jean Rodriguez and Damien Bonne supported by fourteen internationally renowned experts have done an excellent job in covering all aspects of the exciting achievements in the realm of stereoselective MBFTs of the last decade. The book will inspire not only those working in academia to push the forefront of efficient stereoselective synthetic chemistry even further but also chemists in industry to develop and use new one-pot multiple bond-forming cascade protocols for the large-scale synthesis of biologically active compounds, such as pharmaceuticals and agrochemicals.

PREFACE

“

Caminante no hay camino, se hace camino al andar, caminante, son tus huellas el camino y nada más…

”

Antonio Machado, 1875–1939.

The efficiency of a chemical process is now evaluated not only by the yield but also by the amount of waste, the human resources, and the time needed. In simple words, how to make more with less? How to render a synthesis “greener”? In order to address these emerging difficulties, novel organic syntheses must answer as much as possible to economic and environmental problems.

On the basis of these considerations, this book focuses on modern tools for efficient stereoselective synthesis proceeding exclusively with multiple bond-forming transformations (MBFTs), including selected examples of domino, multicomponent, or consecutive sequences within the last ten years. These atom-economic reactions make chemical processes more efficient by decreasing the total number of steps while maximizing the structural complexity and the functional diversity. Moreover, the control of chirality is essential in academic research and also becomes of primary importance in the industrial context such as medicinal chemistry or agrochemical research. For these reasons, we decided to only focus on stereoselective methodologies involving either metallic or organic catalysis and to present some selected current synthetic applications in the field of total synthesis or in the elaboration of biologically relevant targets, including some industrial developments.

We have been particularly exited to embark on this adventure although a bit scared by the challenge of being editors of a book for the first time! However, this has been rapidly overcome with the enthusiastic and friendly collaboration of distinguished experts who have contributed by writing chapters of high scientific level. We are deeply indebted to all authors and coauthors for their rewarding dedication and timely contributions that have enhanced the quality of this book. We are also very honored by the friendly and warm foreword from Dr Dieter Enders. His pioneer achievements and ongoing research in the field of MBFTs is internationally recognized and constitutes an outstanding model for many chemists worldwide. We also gratefully acknowledge the Wiley editorial staff, in particular, Jonathan Rose for his invaluable help and guidance.

Finally, our modest contribution to the field of MBFTs would not have been possible without the strong implication of brilliant PhD students and postdoctoral associates combined with the permanent support of all our colleagues from the group, and we would like here to deeply thank them for their collaboration.

Jean Rodriguez and Damien Bonne, Aix Marseille University, 2015

1DEFINITIONS AND CLASSIFICATIONS OF MBFTs

Damien Bonne and Jean Rodriguez

Aix Marseille Université, CNRS, Marseille, France

1.1 INTRODUCTION

The selective formation of covalent bonds, especially carbon–carbon and carbon–heteroatom bonds, is at the heart of synthetic organic chemistry. From the very beginning, researchers have developed many ingenious methodologies able to create one specific chemical bond at a time, and this has led to very significant advances in the total synthesis of complex natural or nonnatural molecules. Past decades have seen an impressive development of this “step-by-step” approach, notably with the help of efficient catalytic systems, allowing the discovery of new, powerful reactions. This huge investment has been recently rewarded with two Nobel Prizes in chemistry, in 2005 and 2010 [1]. The arsenal of modern organic synthesis is now deep enough for answering “yes” to the question: “can we make this molecule?” provided that sufficient manpower, money, and time are available. However, today's societal economic and ecologic concerns have raised the contemporaneous question: “can we make this molecule efficiently?” This small upgrade places the efficiency of a synthetic pathway in a central position both for academic developments or potential industrial applications. The efficiency of a chemical process is now evaluated not only from the overall yield and selectivity issues but also in terms of the control of waste generation, toxicity and hazard of the chemicals, the level of human resources needed, and the overall time and energy involved: in simple words, “how to make more with less”? How to render a synthesis “greener”?

Clearly, the iterative “step-by-step” approach does not fulfill all these emerging economic and environmental concerns, but it appears that significantly reducing the overall number of synthetic events required to access a defined compound can be a simple strategy to combine together all the above criteria of efficiency. Therefore, “step economy” becomes one of the most important concepts to deal with for the development of efficient modern organic synthetic chemistry.