Organic Reactions, Volume 90

By Wiley

The latest 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: Aug 3, 2016
• ISBN: 9781119291596

Book preview

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 90

About the Author

Chapter 1: The Catalytic, Enantioselective Michael Reaction

Acknowledgments

Introduction

Mechanism and Stereochemistry

Scope and Limitations

Applications to Synthesis

Comparison with Other Methods

Experimental Conditions

Experimental Procedures

Tabular Survey

References

Supplemental References for Table 1A

Supplemental References for Table 1B

Supplemental References for Table 1C

Supplemental References for Table 1D

Supplemental References for Table 2A

Supplemental References for Table 2B

Supplemental References for Table 2D

Supplemental References for Table 3A

Supplemental References for Table 3B

Supplemental References for Table 3C

Supplemental References for Table 3D

Supplemental References for Table 3E

Supplemental References for Table 4A

Supplemental References for Table 4B

Supplemental References for Table 4C

Supplemental References for Table 4D

Supplemental References for Table 5A

Supplemental References for Table 5B

Supplemental References for Table 5C

Supplemental References for Table 5D

Supplemental References for Table 5E

Cumulative Chapter Titles By Volume

Author Index, Volumes 1–90

Chapter and Topic Index, Volumes 1–90

End User License Agreement

List of Illustrations

Chapter 1: The Catalytic, Enantioselective Michael Reaction

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Figure 1 Structure of (DHQ)2PHAL

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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

Vittorio Farina

John Fried

Jacquelyn Gervay-Hague

Heinz W. Gschwend

Stephen Hanessian

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. Rajan Babu

Hans J. Reich

James H. Rigby

William R. Roush

Tomislav Rovis

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 90

Editorial Board

Scott E. Denmark, Editor-in-Chief

Jeffrey Aubé

Carl Busacca

Jin K. Cha

P. Andrew Evans

Paul L. Feldman

Dennis G. Hall

Paul J. Hergenrother

Donna M. Huryn

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

Danielle Soenen, Editorial Coordinator

Landy K. Blasdel, Editorial Assistant

Dena Lindsay, Editorial Assistant

Linda S. Press, Editorial Consultant

Engelbert Ciganek, Editorial Advisor

Associate Editors

Luisa Carrillo

Efraim Reyes

Uxue Uria

Jose L. Vicario

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Published simultaneously in Canada.

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Library of Congress Catalog Card Number: 42-20265

ISBN: 978-1-119-28144-3

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 90

What's in a name?

W. Shakespeare, Romeo and Juliet, (1595) act 2, sc. 2, l. 43

Name reactions! Organic chemists are obsessed with name reactions. Today one can find many compendia (and of course apps) and even an encyclopedia of name reactions, some of which such as Strategic Applications of Named Reactions in Organic Synthesis by László Kürti and Barbara Czakó provide excellent summaries of the genesis, mechanism, and applications of these celebrated transformations. In the preface to Volume 77 I wrote that

the caché associated with a name reaction carries a special significance. Apart from the convenience of being able to identify a given transformation by a simple name and assign credit (whether deserved or not!) to specific individual or individuals, the designation of a name reaction implies a high standard of utility, generality or uniqueness.

Of the 279 chapters published in the Organic Reactions series, 103 are based on name reactions and many others have since become name reactions such as Palladium-Catalyzed Vinylation of Organic Halides in Volume 27 by Richard F. Heck. In addition to the special significance of the transformation, name reactions also raise the obvious question, Who is/was that individual? Apart from historians of science, few practicing chemists and certainly most students actually know who these exceptional people are/were. This is certainly the case for Arthur Michael.

Arthur Michael (1853-1942) was for many years the most versatile and productive American organic chemist, with unrivaled scope and a highly individual view of the theoretical basis of organic chemistry. The son of a prosperous family in Buffalo, New York, he was educated in Germany, Russia, and France and had no college or university degrees except for honorary doctorates. His chemical training abroad resulted in over sixteen papers from Germany starting in 1876 some with S. Gabriel of the University of Berlin faculty and some with other students. His scientific publications numbered 225, appeared over a period of nearly seven decades, and were published from Tufts College, Harvard, or private laboratories which he maintained on the Isle of Wight in 1890s and at Newton Center, Massachusetts, after 1912.

D. S. Tarbell and A. T. Tarbell,

Essays on the History of Organic Chemistry in the United States, 1875-1955,

Folio Publishers: Nashville; 1986, p. 45.

Michael published his first paper on the eponymous reaction simultaneously in German and English in 1887. Ironically, this reaction had already been reported by Ludwig Claisen in 1883 and Michael acknowledged Claisen's priority but he substantially expanded its scope and generality. It can be argued that the Michael Reaction is the first name reaction to be ascribed exclusively to an American organic chemist.

It is therefore not surprising that two chapters covering the Michael Reaction have already appeared in the Organic Reactions series in Volumes 10 (the basic reaction) and 47 (the intramolecular version). The chapter that comprises the current volume by Efraím Reyes, Uxue Uria, Jose L. Vicario, and Luisa Carrillo represents the most advanced variant of this powerful reaction, namely, the catalytic, enantioselective Michael Reaction. The inherent ability of the Michael Reaction to create up to three contiguous stereogenic centers has clearly been recognized and over the course of the past decades, many investigators have learned to control the relative configurations of these newly formed centers. Moreover, the Michael Reaction, thanks in part to its exothermicity, is highly susceptible to catalysis, which in turn has stimulated an enormous amount of activity in the development of chiral catalysts to control both the relative and absolute configurations of the products.

Prof. Vicario and his team have composed an outstanding summary of the most important catalytic variants now available from metal catalysis to organocatalysis. In addition they have provided a detailed description of those pairwise combinations of Michael donor and Michael acceptor that are best suited for a given catalytic mode. The power of this reaction is beautifully illustrated by selected examples in the total synthesis of complex natural products. As is the hallmark of Organic Reactions chapters, the comprehensive coverage found in the Tabular Survey is organized (by donor and acceptor) so that the practitioner hoping to find analogies or precedent for their own work will be quickly directed to the appropriate needle in this massive haystack.

Volume 90 represents the twelfth single chapter volume to be produced in our 75-year history (the third in a row and fifth in the past eleven volumes!). 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 Jeffrey Johnson and P. Andrew Evans who shepherded this chapter to completion. The contributions of the authors, editors, and the publisher were expertly coordinated by the board secretary, Robert M. Coates. In addition, the Organic Reactions enterprise could not maintain the quality of production without the dedicated efforts of its editorial staff, Dr. Danielle Soenen, Dr. Linda S. Press, Dr. Dena Lindsey, and Dr. Landy Blasdel. Insofar as the essence of Organic Reactions chapters resides in the massive tables of examples, the author's and editorial coordinators' painstaking efforts are highly prized.

Scott E. Denmark

Urbana, Illinois

Milan Radoje Uskokovic

July 14, 1924–May 11, 2015

Milan Uskokovic got much of his early life experiences in the crucible that was World War II in Yugoslavia. He promptly joined and fought with the resistance from 1941 through the balance of the conflicts. During this time he developed his characteristic thousand-yard stare, clearly evident in the picture overleaf from 1946.

About the Author

On Saturdays in the 70's at his home in Montclair, NJ, over glasses of doubly-distilled slivovitz and ice, he recollected about the chaos of the times and remembered fondly a short stint in a German POW camp in early 1945 from which he and his colleagues escaped. They told their captors that the resistance was nearby and they would soon be rescued. During the following night, their captors fled. Milan was also involved in rescues of downed American airmen in 1943 and 1944 in resistance-controlled territories. See the published description of Operation Halyard in Freeman, G. A., The Forgotten 500, NAL Caliber (Penguin Group), New York, 2007.

With the ending of hostilities and the beginning of rebuilding his country in 1946, Milan returned to the Polytechnic Institute of the University of Belgrade where he obtained his Diplomate degree in Chemical Engineering. During this period Milan met, studied with, and married a fellow chemical engineering graduate, his beloved Nada.

As Yugoslavia was rebuilt, Milan and Nada worked for several small firms supported by United Nations reconstruction funds, and Milan later landed a manufacturing job in chemistry at Pliva Pharmaceuticals in Zagreb.

In 1956 Milan was awarded a chemistry scholarship for doctoral studies at Clark University in Worcester, Massachusetts. Thanks to the efforts of US Senator Leverett Saltonstall (R-Massachusetts) who arranged for Milan and Nada to immigrate to the US for continued studies. Milan carried out his graduate work with Prof. Ralph I. Dorfman on biologically important steroids useful in the amelioration of pain, lowering blood pressure, and inhibiting contraception. He received his Ph. D. degree from both the Worcester Foundation for Biomedical Research and Clark University in 1960.

Nada and Milan then moved to New Jersey when Milan was offered a position at Hoffmann-LaRoche. Early projects included investigations of 9β,10α-retrosteroids related to dydrogesterone, 19-norsteroids, and azasteroids for a variety of uses, as well as heterocycles in the CNS area. The studies on heterocycles followed the legendary CNS discoveries by Roche's Dr. Leo Sternbach of Librium® (chlordiazepoxide) and Valium® (diazepam) fame.

With Drs. Arnold Brossi and Willi Leimgruber, Milan helped create the Department of Natural Products Chemistry, and began work on a number of biologically active alkaloids including isoquinolines and the important anti-malarial alkaloids which also possessed useful cardiovascular properties. Beginning in 1970, Milan and his group announced several partial and total syntheses of racemic and optically active (−)-quinine and (+)-quinidine. In addition, a technical synthesis was created to convert cheap natural (−)-quinine into the antiarrhythmic agent (+)-quinidine which was marketed as the slow-release glutaconate salt Duraquin® / Quinaglute®.

A collaboration between the Walter Reed Army Hospital and Hoffmann-LaRoche led