Organic Reactions, Volume 88

Table of Contents

Cover

Title Page

Copyright

Introduction to the Series Roger Adams, 1942

Introduction to the Series Scott E. Denmark, 2008

Preface to Volume 88

Chapter 1: Hydroamination of Alkenes

Acknowledgment

Introduction

Mechanism and Stereochemistry

Scope and Limitations

Applications to Synthesis

Comparison with Other Methods

Experimental Conditions

Experimental Procedures

Abbreviations Used in the Tabular Survey

References

Cumulative Chapter Titles by Volume

Author Index, Volumes 1-88

Chapter and Topic Index, Volumes 1-88

End User License Agreement

List of Illustrations

Chapter 1: Hydroamination of Alkenes

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Figure 1 Stereomodels for observed diastereoselectivity in the cyclization of α-substituted aminopentene (left) and aminohexene (right) derivatives.

Advisory Board

John E. Baldwin

Peter Beak

Dale L. Boger

George A. Boswell, Jr.

André B. Charette

Engelbert Ciganek

Dennis Curran

Samuel Danishefsky

Huw M. L. Davies

John Fried

Jacquelyn Gervay-Hague

Heinz W. Gschwend

Stephen Hanessian

Richard F. Heck

Louis Hegedus

Robert C. Kelly

Andrew S. Kende

Laura Kiessling

Steven V. Ley

James A. Marshall

Michael J. Martinelli

Stuart W. McCombie

Jerrold Meinwald

Scott J. Miller

Larry E. Overman

Leo A. Paquette

Gary H. Posner

T. V. RajanBabu

Hans J. Reich

James H. Rigby

William R. Roush

Scott D. Rychnovsky

Martin Semmelhack

Charles Sih

Amos B. Smith, III

Barry M. Trost

Milán Uskokovic

James D. White

Peter Wipf

Former Members of the Board Now Deceased

Roger Adams

Homer Adkins

Werner E. Bachmann

A. H. Blatt

Robert Bittman

Virgil Boekelheide

Theodore L. Cairns

Arthur C. Cope

Donald J. Cram

David Y. Curtin

William G. Dauben

Louis F. Fieser

Ralph F. Hirshmann

Herbert O. House

John R. Johnson

Robert M. Joyce

Willy Leimgruber

Frank C. Mc Grew

Blaine C. Mc Kusick

Carl Niemann

Harold R. Snyder

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

Copyright © 2016 by Organic Reactions, Inc. All rights reserved.

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Library of Congress Catalog Card Number: 42-20265

ISBN: 978-1-119-10385-1

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