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)

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

This volume covers compounds with transition metal—carbon π-bonds for groups 10–8. It is the first volume in the Organometallics category and the first volume of the Science of Synthesis series. The elements covered include Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, and Os and the range of organic π-bonds includes arene, pentadienyl, cyclopentadienyl, diene, allyl, alkyne, and alkene moieties.

The decision to create a series of volumes on organometallics was based on an appreciation of the increasing role that metal complexes play as reagents in organic synthesis. In addition, organometallic complexes are widely used as catalysts or precatalysts in many organic transformations and thus their importance has increased dramatically over the past quarter century.

When work on this volume began, the vision of what Science of Synthesis would aim to do was clearly delineated but the details of how this concept would be implemented were not fully established. As a result, the authors, the volume editor, the series editors, and the staff at the publishing house all worked together to transform the vision into a functioning template for the authors to follow as they searched for data and categorized it before writing their contributions.

The two main issues that had to be resolved for the volumes on organometallics were how to categorize compounds containing more than one type of π-complex and how to include catalytic processes where the π-complex was not isolated but one or more π-complexes were proposed as likely intermediates. The former problem is illustrated by considering a hypothetical cyclopentadienyl–metal–alkene complex where a η⁵ and η² moiety are present. The hierarchical order we used as a guiding principle was that the highest hapticity moiety should take precedence over the lesser hapticity component. This system generally worked well but sometimes the “interesting” part of the molecule (i.e., either the reactive part or the component introduced last) was the lower hapticity element and a reader would be inclined to search under this type of π-complex. In these instances the preparation of the complex might be found in either subsection (or both) of a particular chapter and we hope readers will appreciate that some decision had to be made about what part of the molecule was “interesting” since this often depends on ones perspective!

Both Houben–Weyl and Science of Synthesis are “product based” and this created the potential for problems in including catalytic process. This challenge was addressed by devising a special section under the general heading Applications in Organic Synthesis. Here the authors included examples where π-complexes are proposed but not isolated. The products do not usually contain an organometallic π-bond but their intermediacy is widely accepted and we felt it was necessary to include these reactions if the volume was to be of maximal value.

I would like to thank Guido F. Herrmann and Barry M. Trost for their assistance during the developmental stages of the volume and M. Fiona Shortt and Leigh Murray for professional, efficient, and friendly assistance throughout the entire process. My thanks are extended to my research group who read early drafts of the chapters and offered helpful suggestions and to my young children who waited patiently for me to finish reading galley proofs.

Toronto, June 2001

Volume Editor

Mark Lautens

Volume 1: Compounds with Transition Metal–Carbon π-Bonds and Compounds of Groups 10–8 (Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os)

Preface

Table of Contents

Introduction

M. Lautens

1.1 Product Class 1: Organometallic Complexes of Nickel

J. Montgomery

1.2 Product Class 2: Organometallic Complexes of Palladium

1.2.1 Product Subclass 1: Palladium–Diene Complexes

J. M. Takacs, X. Jiang, and S. Vayalakkada

1.2.2 Product Subclass 2: Palladium–Allyl Complexes

R. W. Friesen

1.2.3 Product Subclass 3: Palladium–Alkyne Complexes

J. M. Takacs, S. Vayalakkada, and X. Jiang

1.2.4 Product Subclass 4: Palladium–Alkene Complexes

J. M. Takacs and S. Vayalakkada

1.3 Product Class 3: Organometallic Complexes of Platinum

A. Ogawa and T. Hirao

1.4 Product Class 4: Organometallic Complexes of Cobalt

M. Malacria, C. Aubert, and J.-L. Renaud

1.5 Product Class 5: Organometallic Complexes of Rhodium

I. Ojima, A. T. Vu, and D. Bonafoux

1.6 Product Class 6: Organometallic Complexes of Iridium

J. M. O’Connor

1.7 Product Class 7: Organometallic Complexes of Iron

1.7.1 Product Subclass 1: Iron–Arene Complexes

G. R. Stephenson

1.7.2 Product Subclass 2: Iron–Dienyl Complexes

G. R. Stephenson

1.7.3 Product Subclass 3: Iron–Diene Complexes

G. R. Stephenson

1.7.4 Product Subclass 4: Iron–Allyl Complexes

G. R. Stephenson

1.7.5 Product Subclass 5: Iron–Alkene Complexes

G. R. Stephenson

1.7.6 Product Subclass 6: Iron–Carbene Complexes

G. R. Stephenson

1.7.7 Product Subclass 7: Iron–Alkyl Complexes

G. R. Stephenson

1.7.8 Product Subclass 8: Ferrocenes

M. Perseghini and A. Togni

1.8 Product Class 8: Organometallic Complexes of Ruthenium

N. Chatani

1.9 Product Class 9: Organometallic Complexes of Osmium

J. Gonzalez and W. D. Harman

Keyword Index

Author Index

Abbreviations

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