Silver in Organic Chemistry E-Book

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

Veröffentlichungsjahr: 2011

Beschreibung

The first authoritative book on using silver cations in organic chemistry—for catalysis and more!

With more sophisticated catalytic methodologies fueling a resurgence in the study of cation-based chemistry, gold and platinum have stepped to the fore as the unique agents used to create new chemical reactions. Although these metals have become a primary focus of researchers in the field, another coinage metal that is often overlooked—but is as powerful as the others—is silver, a far less costly alternative to gold and platinum in aiding the development of new reactions.

Making a strong case for the use of silver as a catalyst and structural element in organometal constructs, this authoritative book is the first to explore the benefits of using silver in organic chemistry by taking a close look at silver’s unique reactivity and structural characteristics for the development of new methods and materials. Silver in Organic Chemistry is:

• The first book to address catalysis using silver, whose use in organic chemistry is on the verge of exploding
• A resource for researchers wishing to do chemistry with silver cations, an area that stands in the shadow of gold chemistry, but still glistens, demonstrating that all that glitters is not gold—sometimes it’s silver!
• A guide for “first attempts” in working with silver cations
• Edited by a very well-respected, highly visible authority in this field

Silver in Organic Chemistry promotes further scientific discussion by offering important new ways to examine the future possibilities of an emerging field. By elevating the importance of silver chemistry, this thought-provoking guide illustrates how this versatile metal can become an increasingly significant player in opening the door to new catalytic organic reactions and new organometal materials.

Leseprobe

Contents

Cover

Title Page

Copyright

Dedication

Foreword

Preface

Contributors

Chapter 1: Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic Synthesis

1.1 Introduction

1.2 Csp3-Ag

1.3 Csp2-Ag

1.4 Csp-Ag

1.5 Conclusion

References

Chapter 2: Cycloaddition Reactions

2.1 Introduction

2.2 [2+2] Cycloadditions

2.3 [3+2] Cycloadditions

2.4 [3+3] Cycloadditions

2.5 [4+2] Cycloadditions

2.6 Concluding Remarks

References

Chapter 3: Sigmatropic Rearrangements and Related Processes Promoted by Silver

3.1 Introduction

3.2 Wolff and Arndt–Eistert Rearrangements and Related Reactions

3.3 Ring Rearrangements

3.4 [3,3]-Sigmatropic Rearrangements

3.5 [2,3]-Sigmatropic Rearrangements

3.6 [1,2]-Sigmatropic Rearrangements

3.7 Miscellaneous

3.8 Conclusion

References

Chapter 4: Silver(I)-Mediated Electrocyclic Processes

4.1 Introduction

4.2 Nucleophilic Trapping of Cationic Intermediates

4.3 The Silver(I)-Promoted Nazarov Reaction

4.4 Concluding Remarks

References

Chapter 5: Silver-Catalyzed Cycloisomerization Reactions

5.1 Introduction

5.2 Cycloisomerization of C=O onto C=C=C

5.3 Cycloisomerization of C=O onto CC

5.4 Cycloisomerization of C=N onto C=C=C

5.5 Cycloisomerization of C=N onto CC

5.6 Ene–Yne Cycloisomerization: C=C onto CC

5.7 Other Transformations

5.8 Conclusion

References

Chapter 6: Silver-Catalyzed Nitrene Transfer Reactions

6.1 Introduction

6.2 Aziridination

6.3 Sulfide and Sulfoxide Imination

6.4 Amidation

6.5 Conclusion

References

Chapter 7: Silver-Catalyzed Silylene Transfer

7.1 Introduction

7.2 Reactivity and Attributes of Metal Silylenoids and Silylmetal Complexes

7.3 Silacyclopropanes as Important Synthetic Intermediates

7.4 Silver-Mediated Transfer of Di-tert-Butylsilylene to Olefins

7.5 Silver-Mediated Transfer of Di-tert-Butylsilylene to Acetylenes

7.6 Silver-Mediated Transfer of Di-tert-Butylsilylene to Carbonyl Compounds

7.7 Silver-Mediated Transfer of Di-tert-Butylsilylene to Imines

7.8 Silver-Mediated Di-tert-Butylsilylene Insertion Into C-O Bonds

7.9 Conclusion

References

Chapter 8: Silver Carbenoids

8.1 Introduction

8.2 Wolff Rearrangement

8.3 Carbene Transfer Reactions to π Bonds

8.4 Formation and Reactions of Ylides

8.5 C–H Insertion

8.6 N–H Insertion

8.7 Ring Expansion Reactions

8.8 Intermediacy of Silver Carbenes

8.9 Miscellaneous Reactions Involving Silver Carbenoids

8.10 Summary

Acknowledgments

References

Chapter 9: Aldol and Related Processes

9.1 Introduction

9.2 Allylation Reaction Using Allyltributyltin

9.3 Allylation Reaction Using Allylsilanes

9.4 Aldol Reaction Using Tin Enolates

9.5 Aldol Reaction Using Silyl enol Ethers

9.6 Mannich Reaction

9.7 Nitrosoaldol Reaction

9.8 Aldol Reaction with Azodicarboxylate

9.9 Conclusion

References

Chapter 10: Coupling Reactions Promoted by Silver

10.1 Introduction

10.2 sp3–sp3 Coupling Reactions Promoted by Silver Salts

10.3 sp3–sp2 Coupling Reactions Promoted by Silver Salts

10.4 sp3–sp Coupling Reactions Promoted by Silver Salts

10.5 sp2–sp2 Coupling Reactions Promoted by Silver Salts

10.6 sp2–sp Coupling Reactions Promoted by Silver Salts

10.7 sp–sp Coupling Reactions Promoted by Silver Salts

10.8 Conclusion

References

Chapter 11: Supramolecular Chemistry of Silver

11.1 Introduction

11.2 Cage-Like Complexes

11.3 Tube-Like Compounds

11.4 Polycatenanes with Silver(I)

11.5 Polyrotaxanes with Silver(I)

11.6 Silver(I) Coordination Polymers with Specific Topology

11.7 Conclusion

Acknowledgments

References

Chapter 12: A Critical Comparison: Copper, Silver, and Gold

12.1 Introduction

12.2 Reactions Catalyzed by Copper, Silver, or Gold

12.3 Reactions Catalyzed by Silver or Gold

12.4 Reactions Catalyzed by Copper or Silver

12.5 Conclusion

References

Index

Copyright © 2010 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:

Silver in organic chemistry / [edited by] Michael Harmata

p. cm.

Includes bibliographical references and index.

ISBN 978-0-470-46611-7 (cloth)

This volume is dedicated to the memories of two outstanding chemists, Dr. Christopher R. Schmid and Dr. Anthony J. Shuker, both of whom succumbed to cancer at an all too early age. Their legacies live on not only in their science but also in those whom they loved, befriended, and inspired.

Foreword

In the last two centuries, the discipline of synthesis has profoundly transformed our world, enabling access to molecules that in former times would be only scarcely or unreliably available from natural sources. Increasingly, synthesis is also being used to access new molecules, designed for function (e.g., catalysts, smart materials, self replicating materials, molecular devices, energy generation and storage systems, diagnostics, drug delivery systems, therapeutics)—many with activities superior to or often different from what nature has produced. We are no longer exclusively reliant on nature for our molecular needs. This too brings new opportunities. Whereas once the challenge in synthesis was simply to make molecules, increasingly that challenge has given away to a more demanding goal: developing strategies that provide molecules in a step economical, and green, if not ideal way. Our ability to meet this goal rests heavily not only on the refinement of existing methodology, but also on the introduction of new reactions and reagents that enable or enhance new synthetic strategies—a focus of this book.

This book explores the use of silver in organic synthesis. Silver and its salts and complexes have figured significantly in the history of chemistry, recognized for their special conductive properties, use in photography, and even biological activities. Notwithstanding the importance of these areas the broader use of silver in chemistry, and more specifically in synthesis, has lagged behind that of other coinage metals. That is changing. One now finds silver as a key component of much that is “nano,” including nano-rods, spheres, sheets, clusters, prisms, membranes, plates, pillars, cubes, bowls, fibers, wires, gels, and sensors. Increasing interest is also being directed at its use and that of other coinage metals in improving synthetic procedures and in enabling new ones. This book provides an insightful overview of how silver figures in these new developments.

Professor Harmata is one of the gifted educators of our time. Through his research and books he has contributed significantly to the advancement of synthesis. For this book, he has assembled a remarkable team of thought leaders who have in their own research contributed significantly to the emerging interest in silver-based reaction science. The resultant product is a must read for those interested in synthesis. It spans impressively from the preparation and use of silver compounds to silver-catalyzed or mediated cycloadditions, rearrangements, isomerizations, group transfers, aldols, and coupling reactions to supramolecular chemistry and comparisons with other metals. It is both an educational and inspirational experience. It has impressive depth and breadth. This contribution to our community sprung in part from frustration with a rejected but clever manuscript title (“All that glitters is not gold”) and the resultant motivation “to do something on behalf of silver.” There is a silver lining to that cloud, as this book on silver in organic chemistry represents a brilliant contribution to the field and an educational experience that is expected to inspire new ideas and glitter for an emerging area of interest.

Paul A. Wender

Stanford University

April 2010

Preface

It was a dark and stormy night….

Editors get to have some fun, don't they? This book was born out of the recognition that there existed no compilation on the power of silver in organic chemistry, particularly synthesis. I recognized this, and within less than a year, while these reviews were being written, a very nice Chemical Reviews issue appeared dedicated to the coinage metals and their importance to organic chemistry. That's life! Such is the pace of developments in the area of coinage metals that those reviews, and those contained herein, will need to be updated within the next few years, however. Have I just suggested that I might take on a second edition of this monograph? I must be nuts.

This book also came about because I am at times pigheaded and not the teddy bear that I am often perceived to be. Not too long ago, I tried to publish a paper that was partially entitled “All that glitters is not gold,” in an effort to do some cheerleading for the silver cation. A referee thought this was an abomination, and my response was less than that of a gentleman and scholar. Fortunately, cooler heads eventually prevailed, the situation was resolved, and the paper was published: I changed the title. However, I was left with the feeling that I needed to do something on behalf of silver, and this book is the result.

My thanks go out to the authors. Through their fine efforts, a very nice monograph has been produced. If this monograph teaches and inspires, even just a little, we will have accomplished our mission.

I must thank Wiley and all the fine folks there for their help and support. My thanks go in particular to Ms. Anita Lekhwan, whose confidence in me and the project never waivered. We all need people to believe in us.

My family has been very patient with me as I put in the extra effort to bring this book to life. My deepest thanks to Judy, Gail, Diana, and Alexander.

Finally, whenever I do a project like this, I like to remind the community that I can make time for this because I have a supported research program. When I began this project, I had both NIH and NSF funding. I will retain the latter for the next few years and hopefully regain the former. A synergistic activity like this allows me to produce a teaching and learning tool and affords me the chance to interact with leading colleagues of the day. Hopefully it adds something to the community; it certainly enriches me.

Michael Harmata

University of Missouri – Columbia

April 2010

Contributors

Zheng-Shuai Bai, Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, China

Philippe Belmont, Equipe “Chimie Organométallique, Hétérocycles et Cibles Biologiques” (COHCB), Institut Curie et CNRS, 26 rue d'Ulm, 75005 Paris, France

Aurélien Blanc, Laboratoire de Synthèse et Réactivité Organiques, Institut de Chimie, Université de Strasbourg, 4 Rue Blaise Pascal, 67000 Strasbourg, France

David A. Capretto, Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, USA

Erick M. Carreira, Laboratory of Organic Chemistry, ETH Zürich, HCI H335, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland

Tom G. Driver, Department of Chemistry, University of Illinois at Chicago, 845W. Taylor St., Chicago, IL 60607, USA

Tina N. Grant, Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, T6G 2G2 Edmonton, Canada

A. Stephen K. Hashmi, Organisch-Chemisches Institut, Ruprecht-Karls-Universität, Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany

Chuan He, Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, USA

Masanori Kawasaki, Medicinal Chemistry Research Laboratories, Pharmaceutical Research Division, Takeda Pharmaceutical Company Limited, 17-85, Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan

Zigang Li, Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, USA

Carl J. Lovely, Department of Chemistry and Biochemistry, The University of Texas at Arlington, 700 Planetarium Place, Arlington, TX 76019, USA

Patrick Pale, Laboratoire de Synthèse et Réactivité Organiques, Institut de Chimie, Université de Strasbourg, 4 Rue Blaise Pascal, 67000 Strasbourg, France

Rebecca H. Pouwer, School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane 4072, Queensland, Australia

Wei-Yin Sun, Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, China

Alex M. Szpilman, Schulich Faculty of Chemistry, Technion—Israel Institute of Technology, 32000 Technion City, Haifa, Israel

Jean-Marc Weibel, Laboratoire de Synthèse et Réactivité Organiques, Institut de Chimie, Université de Strasbourg, 4 Rue Blaise Pascal, 67000 Strasbourg, France

Frederick G. West, Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, T6G 2G2 Edmonton, Canada

Craig M. Williams, School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, 4072 Queensland, Australia

Hisashi Yamamoto, Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, USA

Jin-Quan Yu, Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA

Chapter 1

Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic Synthesis

Rebecca H. Pouwer and Craig M. Williams

School of Chemistry and Molecular Biosciences, University of Queensland, Brisbane, Australia

1.1 Introduction

While the coordination and inorganic chemistry of silver compounds have been prolifically documented, the use of organosilver compounds to effect useful synthetic transformations is severely underrepresented in the synthetic organic chemistry literature. This has prompted us to present a review of literature reporting synthetically useful applications of organosilver compounds in the hope of inspiring further development in this field. The majority of the literature covered in this review concentrates on silver(I) organo-species as reagents, although on some occasions silver(II) and silver “ate” complexes will be discussed, in addition to organosilver intermediates. General reviews encompassing all classes of organosilver compounds have appeared previously.1–3

1.2 Csp3-Ag

1.2.1 Synthesis, Stability, and Reactivity of Alkylsilver Compounds

As a result of extremely low thermal stability, alkylsilver compounds have found only a narrow range of use in organic synthesis. Procedures for the synthesis of alkylsilver compounds as anything but fleeting proposed intermediates are limited to a handful. Semerano and Riccoboni first reported the synthesis of methyl-, ethyl-, and propylsilver in 1941 (Scheme 1.1). Reaction of silver nitrate and the corresponding tetralkyllead in alcohol at −80°C gave the compounds as brown precipitates that decomposed rapidly on warming to room temperature to give metallic silver and a mixture of hydrocarbons.4 This methodology has been utilized in a limited number of investigations into the mechanism of decomposition of alkylsilver compounds.5, 6 In these cases, the presence of the alkylsilver compound, and its subsequent decomposition, is inferred from the isolation of alkyl dimers.

Scheme 1.1

Two plausible mechanistic pathways have been proposed for the thermal decomposition of alkylsilver compounds: either a radically-mediated cleavage of the carbon–silver bond or a process by which the breaking of the silver–carbon bond and formation of the carbon–carbon bond are concerted. Mechanistic studies by Whitesides and coworkers in which the product ratios obtained for the thermal process were compared to those for known radically-mediated reactions have suggested that a concerted process is more likely, although this has not proved to be general.7–9

The formation of methylsilver and dimethylargentate has been observed in the collision-induced dissociation MS3 spectrum of silver diacetate. Dimethylargentate is stable in the gas phase, and has been isolated for short periods (10 s) without significant decomposition.10

Alkylsilver compounds have been prepared by treatment of Grignard reagents with silver salts,11–19 and similarly undergo oxidative homocoupling to give alkyl dimers.11–13, 19, 20 Exploitation of this finding has resulted in the development of general methodology for silver-catalyzed alkyl–alkyl homocoupling of Grignard reagents (Table 1.1).21 The catalytic cycle of this reaction is proposed to proceed via the oxidation of metallic silver with 1,2-dibromoethane to generate silver bromide (Scheme 1.2).

Table 1.1 Silver-Catalyzed Dimerization of Alkylmagesium Halides.

Scheme 1.2

Of particular note is the use of this reactivity to form small carbocycles. Whitesides and coworkers have shown that the treatment of primary bis(alkylmagnesium halides) with tributylphosphinesilver iodide produces carbocycles in a range of yields, with a strong dependence on ring size (Table 1.2). The best results were obtained for four-, five-, and six-membered rings. Although it was hoped that the aggregated nature of alkylsilver compounds would facilitate the formation of medium to large rings, compounds of this type were produced with only low yields.8

Table 1.2 Silver-Mediated Ring-Closing Reaction of Bis(Alkylmagnesium Halides)

It has also been shown that treatment of primary bis(alkylmagnesium halides) with silver trifluoromethanesulfonate effects ring closure under mild conditions for a range of substrates, thus highlighting the generality of this reaction for producing small carbocycles ().