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.

The Editorial Board

October 2000

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

Within the coverage of compounds with one carbon—heteroatom bond (Category 5), the present volume of Science of Synthesis is the first to deal with the heteroatom nitrogen as an element of group 15 of the periodic table. Specifically, the chemistry of aliphatic amines and related organic nitrogen compounds with a formally sp³-hybridized nitrogen is covered and so another important field of organic synthesis is now included in the series.

Following the organizational hierarchy of Science of Synthesis, the emphasis is on the synthesis of amines and related organonitrogen compounds; synthetic applications of the products will be found in the other volumes of Science of Synthesis. However, the specific chemical and biological properties of amines and the related compounds make them attractive targets in themselves. In several examples the amine target is a natural product and so represents an amine in a more complex chemical environment.

The chemistry presented in this volume is extensively reviewed in different volumes of the traditional Houben–Weyl series, especially in Vols. 10/2 (1967), 11/1 (1957), XI/2 (1958) and updated in Vols. E16a (1990), E16c (1992), and E16d, part II (1992). The authors of the present volume have done a great job in culling out the still important information from the old sources and adding to it the new developments, which include improved methods or introduction of novel reagents. This volume demonstrates that today we have a flexible arsenal of methods to synthesize primary, secondary, and tertiary amines, hydroxylamines, and hydrazines including their cyclic or onium derivatives. Moreover, in most cases reliable diastereo- and enantioselective methods to obtain chiral targets are available. If the passing user should be overwhelmed by the multitude of methods, the introductory sections will provide a general orientation and serve as a guideline.

Throughout the development of this volume it was a pleasure to cooperate with the publishing house in Stuttgart. We gratefully acknowledge the input by Dr. Joe Richmond in the planning of the volume and the constant support by Dr. Fiona Shortt de Hernandez and her team, especially Dr. Alex Russell as the responsible scientific editor, but also Dr. Mark Smith, Dr. Marcus White, Dr. Karen Muirhead-Hofmann, and production assistant Michaela Frey, who were always ready to help and have done a great job in making this volume another premium product in the Science of Synthesis series.

Volume Editors

October 2008

Aachen

Clausthal-Zellerfeld

Dieter Enders

Ernst Schaumann

Volume 40a: Amines and Ammonium Salts

Preface

Volume Editors’ Preface

Table of Contents

Introduction

E Schaumann

40.1 Product Class 1: Amino Compounds

40.1.1 Product Subclass 1: Alkyl- and Cycloalkylamines

E Schaumann

40.1.1.1 Synthesis by Reduction

40.1.1.1.1 Reduction of Carbonic and Carboxylic Acid Derivatives

B. Wünsch and C. Geiger

40.1.1.1.2 Reductive Amination of Carbonyl Compounds

P. Margaretha

40.1.1.1.3 Reaction of Acetals with Organometallic Reagents

G K. Friestad

40.1.1.1.4 Hydroaminomethylation of Alkenes

A Börner, M. Beller, and B. Wünsch

40.1.1.1.5 Reduction of Nitrogen-Based Functional Groups

P. Margaretha

40.1.1.2 Synthesis by Substitution

40.1.1.2.1 Synthesis by Substitution of Hydrogen or Metals

H Butenschön

40.1.1.2.2 Substitution of Carbon Functionalities via Solvolysis

F -P. Montforts, M. Osmers, and V. A. Azov

40.1.1.2.3 Substitution of Sulfur or Phosphorus Functionalities

F -P. Montforts and M. Osmers

40.1.1.3 Synthesis by Addition Reactions

40.1.1.3.1 Hydroamination

S. Doye

40.1.1.3.2 Addition of Carbanions to Azomethines

G K. Friestad

40.1.1.3.3 Pericyclic Reactions Involving C=N Units

W. Maison

40.1.1.4 Synthesis by Rearrangement

R. Purchase and M. Sainsbury

40.1.1.5 Synthesis from Other Amino Compounds

40.1.1.5.1 Resolution of Chiral Amines

V. A. Azov

40.1.1.5.2 The Mannich Reaction

J. Ipaktschi and M. R. Saidi

40.1.1.5.3 Modification of Mannich Adducts

J. Ipaktschi and M. R. Saidi

40.1.1.5.4 Substitution on the Amine Nitrogen

S. A. Lawrence

40.1.2 Product Subclass 2: Propargylic Amines

J. Q. Feng and C.-J. Li

40.1.3 Product Subclass 3: Allylic Amines

J. Q. Feng and C.-J. Li

40.1.4 Product Subclass 4: n-Nitroge-n or n-Phosphorus-Functionalized Alkylamines (n >2)

K.-M. Roy

40.1.5 Product Subclass 5: Aziridines

J. B. Sweeney

40.1.6 Product Subclass 6: Azetidines

F. Couty

40.1.7 Product Subclass 7: Ammonium Compounds and Nitrogen Ylides

E. Kruiswijk and J. A. Deck

Keyword Index

Author Index

Abbreviations

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