Cover Page

Advisory Board

  1. John E. Baldwin
  2. Peter Beak
  3. Dale L. Boger
  4. George A. Boswell, Jr.
  5. André B. Charette
  6. Engelbert Ciganek
  7. Dennis Curran
  8. Samuel Danishefsky
  9. Huw M. L. Davies
  10. John Fried
  11. Jacquelyn Gervay-Hague
  12. Heinz W. Gschwend
  13. Stephen Hanessian
  14. Richard F. Heck
  15. Louis Hegedus
  16. Robert C. Kelly
  17. Andrew S. Kende
  18. Laura Kiessling
  19. Steven V. Ley
  20. James A. Marshall
  21. Michael J. Martinelli
  22. Stuart W. McCombie
  23. Jerrold Meinwald
  24. Scott J. Miller
  25. Larry E. Overman
  26. Leo A. Paquette
  27. Gary H. Posner
  28. T. V. RajanBabu
  29. Hans J. Reich
  30. James H. Rigby
  31. William R. Roush
  32. Scott D. Rychnovsky
  33. Martin Semmelhack
  34. Charles Sih
  35. Amos B. Smith, III
  36. Barry M. Trost
  37. Milán Uskokovic
  38. James D. White
  39. Peter Wipf

Former Members of the Board Now Deceased

  1. Roger Adams
  2. Homer Adkins
  3. Werner E. Bachmann
  4. A. H. Blatt
  5. Robert Bittman
  6. Virgil Boekelheide
  7. Theodore L. Cairns
  8. Arthur C. Cope
  9. Donald J. Cram
  10. David Y. Curtin
  11. William G. Dauben
  12. Louis F. Fieser
  13. Ralph F. Hirshmann
  14. Herbert O. House
  15. John R. Johnson
  16. Robert M. Joyce
  17. Willy Leimgruber
  18. Frank C. Mc Grew
  19. Blaine C. Mc Kusick
  20. Carl Niemann
  21. Harold R. Snyder
  22. Boris Weinstein

Organic Reactions

Volume 88

Editorial Board

Scott E. Denmark, Editor-in-Chief

Jeffrey Aubé

Jin K. Cha

André Charette

Vittorio Farina

Paul L. Feldman

Dennis G. Hall

Paul J. Hergenrother

Jeffrey S. Johnson

Marisa C. Kozlowski

Gary A. Molander

John Montgomery

Steven M. Weinreb

Robert M. Coates, Secretary University of Illinois at Urbana-Champaign, Urbana, Illinois

Jeffery B. Press, Secretary Press Consulting Partners, Brewster, New York

Linda S. Press, Editorial Coordinator

Danielle Soenen, Editorial Assistant

Dena Lindsay, Editorial Assistant

Engelbert Ciganek, Editorial Advisor

Associate Editors

Kai C. Hultzsch

Alexander L. Reznichenko

Wiley Logo

Introduction to the Series Roger Adams, 1942

In the course of nearly every program of research in organic chemistry, the investigator finds it necessary to use several of the better-known synthetic reactions. To discover the optimum conditions for the application of even the most familiar one to a compound not previously subjected to the reaction often requires an extensive search of the literature; even then a series of experiments may be necessary. When the results of the investigation are published, the synthesis, which may have required months of work, is usually described without comment. The background of knowledge and experience gained in the literature search and experimentation is thus lost to those who subsequently have occasion to apply the general method. The student of preparative organic chemistry faces similar difficulties. The textbooks and laboratory manuals furnish numerous examples of the application of various syntheses, but only rarely do they convey an accurate conception of the scope and usefulness of the processes.

For many years American organic chemists have discussed these problems. The plan of compiling critical discussions of the more important reactions thus was evolved. The volumes of Organic Reactions are collections of chapters each devoted to a single reaction, or a definite phase of a reaction, of wide applicability. The authors have had experience with the processes surveyed. The subjects are presented from the preparative viewpoint, and particular attention is given to limitations, interfering influences, effects of structure, and the selection of experimental techniques. Each chapter includes several detailed procedures illustrating the significant modifications of the method. Most of these procedures have been found satisfactory by the author or one of the editors, but unlike those in Organic Syntheses, they have not been subjected to careful testing in two or more laboratories. Each chapter contains tables that include all the examples of the reaction under consideration that the author has been able to find. It is inevitable, however, that in the search of the literature some examples will be missed, especially when the reaction is used as one step in an extended synthesis. Nevertheless, the investigator will be able to use the tables and their accompanying bibliographies in place of most or all of the literature search so often required. Because of the systematic arrangement of the material in the chapters and the entries in the tables, users of the books will be able to find information desired by reference to the table of contents of the appropriate chapter. In the interest of economy, the entries in the indices have been kept to a minimum, and, in particular, the compounds listed in the tables are not repeated in the indices.

The success of this publication, which will appear periodically, depends upon the cooperation of organic chemists and their willingness to devote time and effort to the preparation of the chapters. They have manifested their interest already by the almost unanimous acceptance of invitations to contribute to the work. The editors will welcome their continued interest and their suggestions for improvements in Organic Reactions.

Introduction to the Series Scott E. Denmark, 2008

In the intervening years since “The Chief” wrote this introduction to the second of his publishing creations, much in the world of chemistry has changed. In particular, the last decade has witnessed a revolution in the generation, dissemination, and availability of the chemical literature with the advent of electronic publication and abstracting services. Although the exponential growth in the chemical literature was one of the motivations for the creation of Organic Reactions, Adams could never have anticipated the impact of electronic access to the literature. Yet, as often happens with visionary advances, the value of this critical resource is now even greater than at its inception.

From 1942 to the 1980's the challenge that Organic Reactions successfully addressed was the difficulty in compiling an authoritative summary of a preparatively useful organic reaction from the primary literature. Practitioners interested in executing such a reaction (or simply learning about the features, advantages, and limitations of this process) would have a valuable resource to guide their experimentation. As abstracting services, in particular Chemical Abstracts and later Beilstein, entered the electronic age, the challenge for the practitioner was no longer to locate all of the literature on the subject. However, Organic Reactions chapters are much more than a surfeit of primary references; they constitute a distillation of this avalanche of information into the knowledge needed to correctly implement a reaction. It is in this capacity, namely to provide focused, scholarly, and comprehensive overviews of a given transformation, that Organic Reactions takes on even greater significance for the practice of chemical experimentation in the 21st century.

Adams' description of the content of the intended chapters is still remarkably relevant today. The development of new chemical reactions over the past decades has greatly accelerated and has embraced more sophisticated reagents derived from elements representing all reaches of the Periodic Table. Accordingly, the successful implementation of these transformations requires more stringent adherence to important experimental details and conditions. The suitability of a given reaction for an unknown application is best judged from the informed vantage point provided by precedent and guidelines offered by a knowledgeable author.

As Adams clearly understood, the ultimate success of the enterprise depends on the willingness of organic chemists to devote their time and efforts to the preparation of chapters. The fact that, at the dawn of the 21st century, the series continues to thrive is fitting testimony to those chemists whose contributions serve as the foundation of this edifice. Chemists who are considering the preparation of a manuscript for submission to Organic Reactions are urged to contact the Editor-in-Chief.

Preface to Volume 88

The Prefaces to Volumes 78 and 85 highlighted the importance of nitrogen and nitrogen-containing compounds in the biosphere and the “chemosphere”. It is impossible to overstate the enormous diversity of organonitrogen substances as well as their critical role as agrochemicals, pharmaceuticals, and high-performance polymers. Nitrogen is so central to chemistry and life that it has also inspired writers and poets such as Sam Kean (The Disappearing Spoon) and Mario Markus (Chemical Poems: One for Each Element). However, no writer has matched the great Primo Levi in his ability to capture and express the personality and unique character of the elements as found in his classic compendium, The Periodic Table. In the chapter dedicated to Nitrogen, Levi observes:

“Nitrogen is nitrogen, it passes miraculously from the air into plants, from these into animals, and from animals to us; when its function in our body is exhausted, we eliminate it, but it still remains nitrogen, aseptic, innocent. We — I mean to say we mammals — who in general do have problems about obtaining water, have learned to wedge it into the urea molecule, which is soluble in water, and as urea we free ourselves of it; other animals, for whom water is precious, have made the ingenious invention of packaging their nitrogen in the form of uric acid, which is insoluble in water, and of eliminating it as a solid with no necessity of having recourse to water as a vehicle”.

Whereas the chapter that comprised Volume 85 concerned itself with the introduction of nitrogen into aromatic substances through the agency of copper-mediated cross-coupling reactions, the chapter in this volume focuses on the introduction of nitrogen into aliphatic substances, both cyclic and acyclic. Although many such methods have been in use for decades, such as nucleophilic displacement with amines, azides, and nitrites, the most atom-economical method involves the addition of an N–H bond across an unsaturated linkage (alkene, alkyne, allene, diene, etc.). This construct has been the subject of intense investigation only in the past two decades, with a staggering increase in the past ten years. Indeed, the ability to create organonitrogen compounds from alkenes and ammonia may become the modern day equivalent of the Haber-Bosch process which revolutionized agriculture (and unfortunately also warfare).

The success of the research efforts over the past 20 years forms the basis for the single chapter in this volume namely, Hydroamination of Alkenes by Alexander L. Reznichenko and Kai C. Hultzsch. The Board of Editors was hesitant to commission a chapter of this magnitude, but the importance of the chemistry motivated the search for authors with expertise and commitment to undertake such a massive effort. Our hopes could not have been better rewarded. The authors, Drs. Reznichenko and Hultzsch, have compiled an enormous (and growing) literature and distilled it into an extraordinarily useful treatise on all aspects of the hydroamination process. Given the myriad types of unsaturated substrates, metal-based catalysts, and reaction conditions, the authors have done an outstanding job of identifying the best options for various permutations of amine type and alkene structure. This comprehensive treatment of so many different options constitutes a dream “field guide” for the perplexed chemist who wants to know how best to approach the formation of a C-N bond in a target structure to form new stereogenic centers as well as rings of various sizes. Much of the focus in recent years has been on the development of chiral ligand sets for various metals to effect enantioselective hydroaminations. The authors have compiled the state of the art in this field in a scholarly, separate section.

The Tabular Survey is logically organized by substrate structure and further subdivided by inter- and intramolecular reactions as well as enantioselective reactions. This highly user-friendly structure assures the reader to be able to locate relevant precedent with ease. Given the magnitude of this undertaking, the authors had to establish the literature coverage at the outset of the project, January 2011. However, they have provided a supplemental reference list that includes all reports appearing between February 2011 and April 2015.

Volume 88 represents the tenth single-chapter-volume produced in our 73-year history. Such single-chapter volumes represent definitive treatises on extremely important chemical transformations. The organic chemistry community owes an enormous debt of gratitude to the authors of such chapters for the generous contribution of their time, effort, and insights on reactions that we clearly value.

It is appropriate here to acknowledge the expert assistance of the entire editorial board, in particular, André Charette who shepherded this massive chapter to completion. The contributions of the authors, editors, and the publisher were expertly coordinated by the responsible secretaries, Robert Coates and Jeffery Press. In addition, the Organic Reactions enterprise could not maintain the quality of production without the dedicated efforts of its editorial staff, Dr. Linda S. Press, Dr. Danielle Soenen, and Dr. Dena Lindsay. Insofar as the essence of Organic Reactions chapters resides in the massive tables of examples, the authors' and editorial coordinators' painstaking efforts are highly prized.

Scott E. Denmark
Urbana, Illinois