Science of Synthesis

Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis.

Science of Synthesis presents the important synthetic methods for all classes of compounds and includes:

Methods critically evaluated by leading scientists

Background information and detailed experimental procedures

Schemes and tables which illustrate the reaction scope

Preface

As our understanding of the natural world increases, we begin to understand complex phenomena at molecular levels. This level of understanding allows for the design of molecular entities for functions ranging from material science to biology. Such design requires synthesis and, as the structures increase in complexity as a necessity for specificity, puts increasing demands on the level of sophistication of the synthetic methods. Such needs stimulate the improvement of existing methods and, more importantly, the development of new methods. As scientists confront the synthetic problems posed by the molecular targets, they require access to a source of reliable synthetic information. Thus, the need for a new, comprehensive, and critical treatment of synthetic chemistry has become apparent. To meet this challenge, an entirely new edition of the esteemed reference work Houben–Weyl Methods of Organic Chemistry will be published starting in the year 2000.

To reflect the new broader need and focus, this new edition has a new title, Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. Science of Synthesis will benefit from more than 90 years of experience and will continue the tradition of excellence in publishing synthetic chemistry reference works. Science of Synthesis will be a balanced and critical reference work produced by the collaborative efforts of chemists, from both industry and academia, selected by the editorial board. All published results from journals, books, and patent literature from the early 1800s until the year of publication will be considered by our authors, who are among the leading experts in their field. The 48 volumes of Science of Synthesis will provide chemists with the most reliable methods to solve their synthesis problems. Science of Synthesis will be updated periodically and will become a prime source of information for chemists in the 21st century.

Science of Synthesis will be organized in a logical hierarchical system based on the target molecule to be synthesized. The critical coverage of methods will be supported by information intended to help the user choose the most suitable method for their application, thus providing a strong foundation from which to develop a successful synthetic route. Within each category of product, illuminating background information such as history, nomenclature, structure, stability, reactivity, properties, safety, and environmental aspects will be discussed along with a detailed selection of reliable methods. Each method and variation will be accompanied by reaction schemes, tables of examples, experimental procedures, and a background discussion of the scope and limitations of the reaction described.

The policy of the editorial board is to make Science of Synthesis the ultimate tool for the synthetic chemist in the 21st century.

We would like to thank all of our authors for submitting contributions of such outstanding quality, and, also for the dedication and commitment they have shown throughout the entire editorial process.

October 2000

The Editorial Board

D. Bellus (Basel, Switzerland)

E. N. Jacobsen (Cambridge, USA)

S. V. Ley (Cambridge, UK)

R. Noyori (Nagoya, Japan)

M. Regitz (Kaiserslautern, Germany)

P. J. Reider (New Jersey, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

I. Shinkai (Tsukuba, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Volume Editor’s Preface

Ketones are the most important organic compounds in terms of their occurrence and utility in chemical and biochemical transformations and this volume on the synthesis of ketones is the second one of a series of nine volumes of the Science of Synthesis series, covering compounds with two carbon—heteroatom bonds.

This volume has been divided into eleven sections related to a class of ketone (aliphatic and alicyclic ketones, cyclobutanones and cyclopropanones, 1,2-diketones and related compounds, α,α-dihetero- and α-heterosubstituted ketones, ynones, enones, saturated and unsaturated ketones with an additional functional group at α β- or more remote position, and finally saturated and unsaturated ketones with a heteroatom at α β- or more remote position). In all cases, the emphasis is on the formation of the ketone functionality. As aliphatic and alicyclic ketones can be obtained from a great variety of compounds, the section related to these classes of ketone is divided into ten subsections related to the starting material from which these compounds are prepared.

The material has been organized into methods of synthesis of the particular product class, usually with a brief discussion of the scope of the method, followed by specific and selected experimental procedures. In some cases, applications of the method to the preparation of compounds of interest is described. The synthesis of a product class is ordered using the usual Science of Synthesis pattern, with methods and variations within each class in the following order: synthesis by substitution, synthesis by elimination, synthesis by addition reactions (including C—C cleavage), synthesis by rearrangement. The coverage of the methods is not exhaustive, rather the most reliable methods for the synthesis of each class of ketones has been selected and a preference has been given to the more recent methods.

I would like to thank all of the authors, who had to read a large amount of publications and to extract and abstract the most important information to be included in their chapter. I would like to thank Prof. E. J. Thomas and Dr Joe Richmond for their help in planning and organizing this volume. Many thanks also to Prof. E. J. Thomas for his advice and comments. My thanks are also to Dr Fiona Shortt de Hernandez, Leigh Murray, Dr Mark Smith and to all the editors at Thieme, Dr K. L. Greenfield, Dr Karen Muirhead, Dr E. Smeaton and Dr C. Twomey for their professional and friendly assistance throughout the entire process of this book. It was a great pleasure for me to work with all of them.

Paris, November 2004

Volume Editor

Janine Cossy

Volume 26: Ketones

Preface

Volume Editors’ Preface

Table of Contents

Introduction

J. Cossy

26.1 Product Class 1: Aliphatic and Alicyclic Ketones (Excluding Cyclobutanones and Cyclopropanones)

P. Vogel

26.1.1 Synthesis by Oxidation of Heterosubstituted Alkanes

S. von Angerer

26.1.2 Synthesis by Oxidation of Alkenes and Alkanes (Excluding Allylic or Benzylic Derivatives)

T. S. Balaban

26.1.3 Synthesis by Reduction of 1,2-Diketones and α-Diazo Ketones, α,α-Dihetero- and α-Heterosubstituted Ketones, Enones, and Ynones

M. Yus and C. Nájera

26.1.4 Synthesis from Carboxylic Acids and Derivatives by Substitution with a Carbon Nucleophile

B. Figadère and X. Franck

26.1.5 Synthesis from Aldehydes by Substitution of the Aldehyde Hydrogen

B. Figadère and X. Franck

26.1.6 Synthesis from Thioketones, Acetals, Cyanohydrins, Enol Ethers, Enamines, Other Ene Derivatives, and Related Compounds

D. Desmaële

26.1.7 Synthesis by Addition

B. Figadère and X. Franck

26.1.8 Synthesis by Fragmentation and Rearrangement

T. Constantieux and J. Rodriguez

26.1.9 Synthesis from Other Ketones

J.-C. Plaquevent, D. Cahard, and F. Guillen

26.1.10 Synthesis from Enones by Formation of C—C Bonds

J.-C. Plaquevent, D. Cahard, and F. Guillen

26.2 Product Class 2: Cyclobutanones and Their Precursors

J. Salaün

26.3 Product Class 3: Cyclopropanones and Their Precursors

J. Salaün

26.4 Product Class 4: 1,2-Diketones and Related Compounds

Y. Landais and J. M. Vincent

26.5 Product Class 5: α,α-Diheterosubstituted Ketones

J.-L. Parrain and J. Thibonnet

26.6 Product Class 6: α-Heterosubstituted Ketones

J. Suffert

26.7 Product Class 7: Ynones

A. Nelson

26.8 Product Class 8: Aryl Ketones

J. M. Campagne and Y. Six

26.9 Product Class 9: Enones

S. P. Marsden

26.10 Product Class 10: Saturated or Unsaturated Ketones with an Additional Carbonyl, Nitrile, or Carboxy Substituent or Equivalent at a ß or More Remote Position: Synthesis of the Ketone Functionality

I. Chataigner, A. Harrison-Marchand, and J. Maddaluno

26.11 Product Class 11: Saturated and Unsaturated Ketones Containing a β- or More Remote Heteroatom Substituent

A. Harrison-Marchand, I. Chataigner, and J. Maddaluno

Keyword Index

Author Index

Abbreviations

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