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

Heteroatom- and in particular halogen- and oxygen-substituted alkenes are of central importance in all fields of synthetic organic chemistry. One has just to think about enolates, enol ethers, vinyl trifluoromethanesulfonates, and vinyl halides and their enormous potential for undergoing carbon–carbon and carbon–heteroatom couplings to appreciate the value of this volume within the well-established series of Science of Synthesis. Additionally, a variety of less common but equally important heteroatom-substituted alkenes and allenes are covered in detail.

I would like to express my personal thanks to the many authors who have given their expertise, time, and commitment. It was a pleasure to plan the volume with the exceptional experience and insight provided by Prof. Ernst Schaumann and Dr. Joe Richmond, and to bring it into existence with the immense support of the Thieme editorial team headed by Dr. Fiona Shortt de Hernandez. In particular, I thank Dr. Marcus White for his relentless efforts to get all the chapters delivered, completed, organized, and corrected within a reasonable span of time.

Vienna, August 2008

Volume Editor

Johann Mulzer

Table of Contents

Introduction

J. Mulzer

Introduction

32.1 Product Class 1: 1,3-Bis(heteroatom-substituted) Allenes and Analogous Higher Cumulenes

A. S. K. Hashmi

32.1 Product Class 1: 1,3-Bis(heteroatom-substituted) Allenes and Analogous Higher Cumulenes

32.1.1 Product Subclass 1: 1,3-Dihaloallenes

32.1.1.1 Synthesis of Product Subclass 1

32.1.1.1.1 Method 1: Synthesis Using Alkyllithium Reagents and Pyran-2-ones

32.1.2 Product Subclass 2: 1-Halo-3-(organooxy)allenes

32.1.3 Product Subclass 3: 1-Halo-3-(organochalcogeno)allenes

32.1.3.1 Synthesis of Product Subclass 3

32.1.3.1.1 Method 1: Synthesis Using Sulfonoselenoate Reagents and Alkynes

32.1.4 Product Subclass 4: 1-Nitrogen-Functionalized 3-Haloallenes

32.1.5 Product Subclass 5: 1-Phosphorus-Functionalized 3-Haloallenes

32.1.6 Product Subclass 6: 1,3-Bis(organooxy)allenes

32.1.7 Product Subclass 7: 1-(Organochalcogeno)-3-(organooxy)allenes

32.1.7.1 Synthesis of Product Subclass 7

32.1.7.1.1 Method 1: Synthesis Using Silyl Ketene Reagents and Alkynes

32.1.8 Product Subclass 8: 1-Nitrogen-Functionalized 3-(Organooxy)allenes

32.1.9 Product Subclass 9: 1-Phosphorus-Functionalized 3-(Organooxy)allenes

32.1.10 Product Subclass 10: 1,3-Bis(organochalcogeno)allenes

32.1.11 Product Subclass 11: 1-Nitrogen-Functionalized 3-(Organochalcogeno)-allenes

32.1.12 Product Subclass 12: 1-Phosphorus-Functionalized 3-(Organochalcogeno)-allenes

32.1.13 Product Subclass 13: 1,3-Bis(nitrogen-functionalized) Allenes

32.1.14 Product Subclass 14: 1-Nitrogen-Functionalized 3-Phosphorus-Functionalized Allenes

32.1.15 Product Subclass 15: 1,3-Bis(phosphorus-functionalized) Allenes

32.1.16 Product Subclass 16: 1,ω-Bis(heteroatom-functionalized) Cumulenes

32.2 Product Class 2: Monofunctionalized Allenes and Higher Cumulenes

A. S. K. Hashmi

32.2 Product Class 2: Monofunctionalized Allenes and Higher Cumulenes

32.2.1 Product Subclass 1: Haloallenes

32.2.1.1 Synthesis of Product Subclass 1

32.2.1.1.1 Method 1: Fluoroallenes by Fluoride Substitution with Organocuprates

32.2.1.1.2 Method 2: Chloroallenes by Isomerization of Propargylic Chlorides

32.2.1.1.2.1 Variation 1: Using a Copper(I)/Copper(0) Catalyst

32.2.1.1.2.2 Variation 2: Using Only a Copper(I) Catalyst

32.2.1.1.3 Method 3: Chloroallenes from Propargylic Alcohols and Thionyl Chloride

32.2.1.1.4 Method 4: Chloroallenes from Propargylic Alcohols and Hydrogen Chloride

32.2.1.1.5 Method 5: Flash-Vacuum Thermolysis of 1-Chlorocyclopropenes

32.2.1.1.6 Method 6: Chloroallenes from Benzyne and Propargyl Chloride

32.2.1.1.7 Method 7: Chloroallenes from Ketene Silyl Acetals

32.2.1.1.8 Method 8: Chloroallenes from Alkynes and Benzil

32.2.1.1.9 Method 9: Chloroallenes from Propargylic Alcohols and Titanium(IV) Chloride

32.2.1.1.10 Method 10: Bromoallenes by Alkynylogous Ring Opening of Oxiranes

32.2.1.1.11 Method 11: Bromoallenes by Copper-Mediated Nucleophilic Substitution of Propargylic Methanesulfonates

32.2.1.1.12 Method 12: Bromoallenes from Acid Chlorides

32.2.1.1.13 Method 13: Bromoallenes from Phosphonium Bromides

32.2.1.1.14 Method 14: Iodoallenes from Propargylic Alcohols

32.2.1.1.14.1 Variation 1: Activation of the Propargylic Alcohol by a Phosphonium Species

32.2.1.1.14.2 Variation 2: Using a Copper(I)/Copper(0) Catalyst

32.2.2 Product Subclass 2: (Organochalcogeno)allenes

32.2.2.1 Synthesis of Product Subclass 2

32.2.2.1.1 Method 1: Isomerization of Propargyl Ethers by Potassium tert-Butoxide/tert-Butyl Alcohol

32.2.2.1.2 Method 2: Isomerization of Propargyl Ethers by Potassium tert-Butoxide/Pentane

32.2.2.1.3 Method 3: Isomerization–Elimination of Propargyl Ethers by Potassium tert-Butoxide/Benzene

32.2.2.1.4 Method 4: Metalation of Alkoxyallenes and Addition to Aldehydes

32.2.2.1.5 Method 5: Alkylation of the Intermediate Obtained from Acylsilanes and Acetylides

32.2.2.1.6 Method 6: Wittig Alkenation of Chromium–Carbene Complexes

32.2.2.1.7 Method 7: Alkylation–Isomerization of Propargyl Sulfides

32.2.2.1.8 Method 8: Allenyl Sulfides and Selenides by the Wittig Route

32.2.2.1.9 Method 9: Allenyl Sulfides by a Three-Component Reaction

32.2.2.1.10 Method 10: Allenyl Sulfides by Palladium-Catalyzed Coupling

32.2.3 Product Subclass 3: Nitrogen-Functionalized Allenes

32.2.3.1 Synthesis of Product Subclass 3

32.2.3.1.1 Method 1: Allenyl Amides by Base-Catalyzed Rearrangement

32.2.3.1.2 Method 2: Morpholinoallenes by Conjugate Addition

32.2.3.1.3 Method 3: 4-Vinylideneoxazolidin-2-ones by Palladium Catalysis

32.2.3.1.4 Method 4: Copper-Catalyzed Coupling of Allenyl Halides with Amides, Carbamates, and Ureas

32.2.3.1.5 Method 5: Rhodium-Catalyzed Coupling of Propargylic Carbonates and Sulfonamides

32.2.4 Product Subclass 4: Phosphorus-Functionalized Allenes

32.2.4.1 Synthesis of Product Subclass 4

32.2.4.1.1 Method 1: Isomerization of Propargylphosphines under Basic Conditions

32.2.5 Product Subclass 5: Monofunctionalized Cumulenes

32.2.5.1 Synthesis of Product Subclass 5

32.2.5.1.1 Method 1: Wittig Route to Bromobutatrienes

32.2.5.1.2 Method 2: Elimination/Deprotonation/Regioselective Reprotonation

32.3 Product Class 3: 1,2-Bis(heteroatom-substituted) Alkenes

32.3.1 Product Subclass 1: 1,2-Dihaloalkenes

U. Nubbemeyer

32.3.1 Product Subclass 1: 1,2-Dihaloalkenes

32.3.1.1 Synthesis of Product Subclass 1

32.3.1.1.1 Method 1: Synthesis by Oxidation of Arenes or Hetarenes

32.3.1.1.1.1 Variation 1: Oxidation of 3,4-Dibromo-2,5-bis(phenylsulfanyl)furan

32.3.1.1.1.2 Variation 2: Oxidation of Halogenated Azatriquinacenes

32.3.1.1.1.3 Variation 3: Oxidation of Phenols

32.3.1.1.1.4 Variation 4: Oxidation of Aniline

32.3.1.1.2 Method 2: Synthesis by Reduction

32.3.1.1.2.1 Variation 1: Reductive Defluorination

32.3.1.1.2.2 Variation 2: Reductive Dechlorination

32.3.1.1.2.3 Variation 3: Reductive Elimination of Mixed Halogen Atoms

32.3.1.1.2.4 Variation 4: Reductive Coupling

32.3.1.1.3 Method 3: Synthesis by Substitution

32.3.1.1.3.1 Variation 1: Substitution of Fluorine

32.3.1.1.3.2 Variation 2: Substitution of Chlorine or Bromine Atoms

32.3.1.1.3.3 Variation 3: Substitution of Halogens by Alkyl or Aryl Groups

32.3.1.1.3.4 Variation 4: Substitution of Oxygen

32.3.1.1.4 Method 4: Synthesis by Elimination

32.3.1.1.4.1 Variation 1: Dehydrofluorination

32.3.1.1.4.2 Variation 2: Dehydrochlorination

32.3.1.1.4.3 Variation 3: Dehydrobromination

32.3.1.1.4.4 Variation 4: Dehydroiodination

32.3.1.1.4.5 Variation 5: Elimination of Sulfur

32.3.1.1.4.6 Variation 6: Elimination with Fragmentation

32.3.1.1.5 Method 5: Synthesis by Addition

32.3.1.1.5.1 Variation 1: Addition of Methyl Hypofluorite to Allenes or Butadienes

32.3.1.1.5.2 Variation 2: Addition of Chlorine to Alkynes

32.3.1.1.5.3 Variation 3: Addition of Bromine to Alkynes

32.3.1.1.5.4 Variation 4: Addition of Iodine to Alkynes

32.3.1.1.5.5 Variation 5: Addition of Bromine Monofluoride to Alkynes

32.3.1.1.5.6 Variation 6: Addition of an Iodine and a Fluorine Atom to Alkynes

32.3.1.1.5.7 Variation 7: Addition of Halogen Chlorides or Halogen Bromides to Alkynes

32.3.1.1.5.8 Variation 8: Addition of Nucleophiles to vic-Dihaloquinones and Related Systems

32.3.1.1.5.9 Variation 9: Carbene Dimerization

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