Organic Reactions, Volume 94

By Wiley

The 94th volume in this series for organic chemists in industry presents critical discussions of widely used organic reactions or particular phases of a reaction. The material is treated from a preparative viewpoint, with emphasis on limitations, interfering influences, effects of structure and the selection of experimental techniques. The work includes tables that contain all possible examples of the reaction under consideration. Detailed procedures illustrate the significant modifications of each method.

• Language: English
• Publisher: Wiley
• Release date: Nov 8, 2017
• ISBN: 9781119361190

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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 94

Chapter 1: [3 + 2] Dipolar Cycloadditions of Cyclic Nitrones with Alkenes

Acknowledgments

Introduction

Mechanism and Stereochemistry

Scope and Limitations

Applications to Synthesis

Comparison with Other Methods

Experimental Conditions

Experimental Procedures

Tabular Survey

References

Cumulative Chapter Titles By Volume

Author Index, Volumes 1–94

Chapter and Topic Index, Volumes 1–94

End User License Agreement

List of Illustrations

Chapter 1: [3 + 2] Dipolar Cycloadditions of Cyclic Nitrones with Alkenes

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Figure 1 HOMO-LUMO inteactions with electron-rich dipolarophiles.

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Figure 2 HOMO-LUMO inteactions with electron-poor dipolarophiles.

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Figure 3 Transition state trajectories for intermolecular cycloadditions leading to stereodifferentiated constitutional isomers.

Figure 4 Possible transition states and products for the cycloaddtion of 5-membered cyclic nitrones and monosubstituted alkenes.

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Figure 5 Examples of polyhydroxylated enantiopure 5-membered cyclic nitrones derived from the chiral pool.

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Figure 6 Examples of polyhydroxylated enantiopure six-membered cyclic nitrones derived from the chiral pool.

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Figure 7 Examples of seven- and eight-membered cyclic nitrones used in cycloaddition reactions.

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Figure 8 Examples of palladium-, iron-, and rethenium-based catalysts used in cycloaddtion reactions.

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Figure 9 Examples of rhodium- and iridium-based catalysts used in cycloaddtion reactions.

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Figure 10 Examples of chiral half-sandwich ruthenium complexes used in cycloaddition reactions.

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Figure 11 Types of intramolecular 1,3-dipolar cycloadditions of five-membered (Type a) and six-membered (Type b) cyclic nitrones with tethered alkenes (the tether in the substrates is depicted in bold, as is the newly formed ring that contains the tether in the adducts; Tether Length: number of all the atoms between the cyclic nitrone C(2) and the dipolarophile).

Figure 12 Examples of classification of constitutionally isomeric cycloadducts according to the size of the nitrone ring (six in the examples), the isoxazolidine ring (five) and the ring containing the tether (seven and eight, show in bold).

Figure 13 Examples of Type Ia and IIa intramolecular 1,3-dipolar cycloadditions of 5-membered cyclic nitrones with a three-atom tethered alkene (tether shown in bold).

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Advisory Board

John E. Baldwin

Peter Beak

Dale L. Boger

André B. Charette

Engelbert Ciganek

Dennis Curran

Samuel Danishefsky

Huw M. L. Davies

John Fried

Jacquelyn Gervay-Hague

Heinz W. Gschwend

Stephen Hanessian

Louis Hegedus

Paul J. Hergenrother

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

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

George A. Boswell, Jr.

Theodore L. Cairns

Arthur C. Cope

Donald J. Cram

David Y. Curtin

William G. Dauben

Richard F. Heck

Louis F. Fieser

Ralph F. Hirshmann

Herbert O. House

John R. Johnson

Robert M. Joyce

Willy Leimgruber

Frank C. McGrew

Blaine C. McKusick

Carl Niemann

Harold R. Snyder

Milán Uskokovic

Boris Weinstein

Organic Reactions

Volume 94

Editorial Board

Scott E. Denmark, Editor-in-Chief

Jeffrey Aubé

David B. Berkowitz

Carl Busacca

Jin K. Cha

P. Andrew Evans

Paul L. Feldman

Dennis G. Hall

Donna M. Huryn

Marisa C. Kozlowski

Gary A. Molander

John Montgomery

Albert Padwa

Tomislav Rovis

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

Danielle Soenen, Editorial Coordinator

Landy K. Blasdel, Editorial Assistant

Dena Lindsay, Editorial Assistant

Linda S. Press, Editorial Consultant

Engelbert Ciganek, Editorial Advisor

Associate Editors

Alberto Brandi

Francesca Cardona

Stefano Cicchi

Franca M. Cordero

Andrea Goti

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Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

ISBN: 978-1-119-30893-5

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 94

"If we take into account the close relationship between carboxylic acids and nitronic acids, we shall come to the following comparison of the corresponding C and N compounds. The designation nitrone for the compounds of the type R¹R²=N=O becomes readily comprehensible.."

P. Pfeiffer, Annalen 1916, 411, 72

The 76-year history of the Organic Reactions series serves not only as a treasure trove of knowledge but also as a chronicle of the progress of synthetic organic chemistry. In our current state of oversaturation and obsession with the latest report or incremental advance, we become immune to the realization of how much progress has been made in such a short period of time. Casual perusal of the more than 200 chapters in the series reveals the incredible structure of vertical science, a perspective difficult to perceive in a culture wherein scholarly outlets compete for immediate attention.

One of the most compelling illustrations of the progress of this discipline can be seen in the evolution of various reactions that have been documented several times in our history. Compare for example the chapter on the Aldol Condensation in Volume 16 (1968) with that on Catalytic, Enantioselective Aldol Reactions in Volume 67 (2006) or even more dramatically, the chapter on the Schmidt Reaction in Volume 3 (1946) and the update by the same name in Volume 78 (2012). Reading these chapters provides a welcome calibration on the health and power of synthesis and also invites the unavoidable question, quo vadis what will chemists be able to accomplish 50 years hence?

The single chapter in Volume 94 provides another such landmark, and one that is all the more remarkable because it provides an update on an even more recent chapter than those mentioned above. The combination of Rolf Huisgen's early studies on reactions of dipoles, along with the brilliant insights of Woodward and Hoffmann on the foundational theory of pericyclic reactions, has led to a universe of powerful transformations belonging the family of dipolar cycloadditions. One of the most synthetically useful members of this family is the [3+2] cycloaddition of nitrones which was the topic of a definitive chapter in Volume 36 (1988) authored by Pat Confalone and Edward Huie. Now, nearly 30 years later, this reaction has grown to be so valuable in organic synthesis that a similarly comprehensive treatment has become impossible. Nevertheless, we are