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

Volume 31 of Science of Synthesis is concerned with substituted arenes of the type Ar—X, where X are functional groups in which the arene ring is bonded to a F, Cl, Br, I, O, S, Se, Te, N, or P atom. At a very early stage in its life, and to the surprise of the newly appointed Volume Editor, Volume 31 underwent mitosis and became Volumes 31a (F, Cl, Br, I, O, S, Se, Te) and 31b (N, P). The combined size of Volumes 31a and 31b is an indication of the extent and importance of this area of organic chemistry. There can be few, if any, synthetic laboratories or chemical manufacturers who do not routinely handle intermediates or products of the type Ar—X. The subject has developed over approximately 175 years and important developments have taken place at regular intervals throughout this period, including the last decade. The various methods of forming Ar—X bonds, together with the rich chemistry of arene functional group interconversion, cover most of the important principles of modern organic chemistry.

I am particularly grateful to Dr. Daniel Bellus and Dr. Joe Richmond who greatly assisted in the early planning of the volume, especially during a convivial January weekend in Stuttgart. I also thank Dr. Fiona Shortt de Hernandez and all the members of her editorial team at Thieme. I particularly thank Dr. Matthew Weston, Dr. Mark Smith, and Dr. Marcus White for their help and advice throughout the editorial process and also Angela Gilden and Michaela Frey for their smooth handling of commissioning and proofreading. Finally, I most warmly thank all the authors of Volume 31 who accepted the challenge of surveying one of the oldest and largest areas of organic chemistry and with their extensive experience and expertise have collectively produced a comprehensive and authoritative account of arene chemistry.

Volume Editor

Chris Ramsden

Keele, May 2007

Table of Contents

Introduction

C. A. Ramsden

Introduction

31.1 Product Class 1: Fluoroarenes

G. Sandford

31.1 Product Class 1: Fluoroarenes

31.1.1 Synthesis of Product Class 1

31.1.1.1 Synthesis by Substitution of Hydrogen

31.1.1.1.1 Method 1: Direct Fluorination with Elemental Fluorine

31.1.1.1.2 Method 2: Reaction with Electrophilic N—F Reagents

31.1.1.1.2.1 Variation 1: With 1-Fluoropyridinium Salts

31.1.1.1.2.2 Variation 2: With 1-(Chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]-octane Bis(tetrafluoroborate)

31.1.1.1.2.3 Variation 3: With Other Electrophilic N—F Reagents

31.1.1.1.3 Method 3: Reaction with Xenon Difluoride

31.1.1.1.4 Method 4: Reaction with Organic Hypofluorites

31.1.1.1.5 Method 5: Reaction with Cesium Fluoroxysulfate

31.1.1.2 Synthesis by Substitution of Organometallic Groups

31.1.1.2.1 Method 1: Reaction of Aryllithium Derivatives

31.1.1.2.2 Method 2: Reaction of Phenylmagnesium Halides

31.1.1.2.3 Method 3: Reactions of Aryl–Group 14 Derivatives

31.1.1.3 Synthesis by Substitution of Halogen Atoms

31.1.1.3.1 Method 1: Reaction with Alkali Metal Fluorides

31.1.1.4 Synthesis by Substitution of Sulfur

31.1.1.4.1 Method 4: Reaction of Sulfonyl Derivatives

31.1.1.5 Synthesis by Substitution of Nitrogen

31.1.1.5.1 Method 1: Replacement of Nitro Groups

31.1.1.5.1.1 Variation 1: Reaction with Potassium Fluoride

31.1.1.5.1.2 Variation 2: Reaction with Tetraalkylammonium Fluorides

31.1.1.5.2 Method 2: Replacement of Diazo Groups

31.1.1.5.2.1 Variation 1: Reaction with Hydrogen Fluoride

31.1.1.5.2.2 Variation 2: Reaction with Hydrogen Fluoride/Pyridine Mixtures

31.1.1.5.2.3 Variation 3: Reaction of Diazonium Tetrafluoroborates

31.1.1.5.2.4 Variation 4: Reaction of Diazonium Hexafluoroantimonates

31.1.1.5.2.5 Variation 5: Reaction with Nitrosonium Tetrafluoroborate

31.1.1.5.2.6 Variation 6: Reaction of Triazenes

31.1.1.6 Synthesis by Elimination

31.1.1.6.1 Method 1: Elimination of Hydrogen Fluoride

31.1.1.6.2 Method 2: Elimination of Fluorine

31.1.1.7 Synthesis with Retention of Fluorine

31.1.1.7.1 Method 1: Reactions of Fluoroarenes

31.1.1.7.2 Method 2: Reactions of Perfluoroarenes

31.2 Product Class 2: Chloroarenes

S. P. Stanforth

31.2 Product Class 2: Chloroarenes

31.2.1 Synthesis of Product Class 2

31.2.1.1 Synthesis by Substitution

31.2.1.1.1 Method 1: Electrophilic Chlorination

31.2.1.1.1.1 Variation 1: Of Phenols and Anisoles

31.2.1.1.1.2 Variation 2: Of Anilines and Acetanilides

31.2.1.1.1.3 Variation 3: Of Alkylbenzenes

31.2.1.1.1.4 Variation 4: Of Polycyclic Aromatics

31.2.1.1.2 Method 2: The Sandmeyer Reaction

31.2.1.1.3 Method 3: Substitution of a Nitro Group

31.2.1.1.4 Method 4: Substitution of a Phenolic Hydroxy Group

31.2.1.2 Synthesis by Elimination

31.2.1.2.1 Method 1: Dehydrohalogenation

31.2.1.2.2 Method 2: Dehalogenation

31.2.1.2.3 Method 3: Pyrolytic Loss of a Small Molecule

31.2.1.2.4 Method 4: Transition-Metal-Catalyzed Decarbonylation

31.2.1.3 Synthesis by Cycloaddition

31.2.1.3.1 Method 1: Cycloadditions Reactions of Tetrachlorothiophene Dioxide

31.2.1.3.2 Method 2: Cobalt-Catalyzed Reactions

31.2.1.4 Synthesis by Rearrangement

31.2.1.4.1 Method 1: Rearrangement During Chlorination

31.2.2 Applications of Product Class 2 in Organic Synthesis

31.2.2.1 Method 1: Cross-Coupling Reactions

31.2.2.1.1 Variation 1: Synthesis of Biaryls

31.2.2.1.2 Variation 2: Synthesis of Arylalkenes

31.2.2.1.3 Variation 3: Synthesis of Arylalkynes

31.2.2.1.4 Variation 4: Synthesis of Arylalkanes

31.2.2.1.5 Variation 5: Carbonylation and Cyanation Reactions

31.2.2.1.6 Variation 6: Metal-Catalyzed Heterosubstitution Reactions

31.2.2.2 Method 2: Nucleophilic Substitution Reactions

31.2.2.2.1 Variation 1: The SNAr Reaction

31.2.2.2.2 Variation 2: The SRN1 Reaction

31.2.2.2.3 Variation 3: Substitution via Benzyne Intermediates

31.2.2.3 Method 3: Enzymatic Oxidation Reactions

31.3 Product Class 3: Bromoarenes

S. P. Stanforth

31.3 Product Class 3: Bromoarenes

31.3.1 Synthesis of Product Class 3

31.3.1.1 Synthesis by Substitution

31.3.1.1.1 Method 1: Electrophilic Bromination

31.3.1.1.1.1 Variation 1: Of Phenols and Anisoles

31.3.1.1.1.2 Variation 2: Of Anilines

31.3.1.1.1.3 Variation 3: Of Benzene and Alkylbenzenes

31.3.1.1.1.4 Variation 4: Of Deactivated Benzenes

31.3.1.1.1.5 Variation 5: Of Polycyclic Aromatics

31.3.1.1.2 Method 2: Synthesis from Organometallics

31.3.1.1.2.1 Variation 1: From Aryllithiums

31.3.1.1.2.2 Variation 2: From Arylsilanes

31.3.1.1.2.3 Variation 3: From Arylstannanes

31.3.1.1.3 Method 3: The Sandmeyer Reaction

31.3.1.1.4 Method 4: Substitution of a Phenolic Group

31.3.1.2 Synthesis by Elimination

31.3.1.2.1 Method 1: Dehydrohalogenation

31.3.1.2.2 Method 2: Dehalogenation

31.3.1.2.3 Method 3: Transition-Metal-Catalyzed Decarbonylation

31.3.1.2.4 Method 4: The Cristol–Firth–Hunsdiecker Reaction

31.3.1.3 Synthesis by Cycloaddition

31.3.2 Applications of Product Class 3 in Organic Synthesis

31.3.2.1 Cross-Coupling Reactions

31.3.2.1.1 Method 1: Synthesis of Biaryls

31.3.2.1.2 Method 2: Synthesis of Arylalkenes

31.3.2.1.3 Method 3: Synthesis of Arylalkynes

31.3.2.1.4 Method 4: Synthesis of Arylalkanes

31.3.2.1.5 Method 5: Carbonylation and Cyanation Reactions

31.3.2.1.6 Method 6: Metal-Catalyzed Heterosubstitution Reactions

31.3.2.2 Nucleophilic Substitution Reactions

31.3.2.2.1 Method 1: The SNAr Reaction

31.3.2.2.2 Method 2: The SRN1 Reaction

31.3.2.2.3 Method 3: Substitution via Benzyne Intermediates

31.3.2.3 Generation of Aryl Radicals

31.3.2.4 Generation of Organometallic Reagents

31.3.2.5 Enzymatic Oxidation Reactions

31.4 Product Class 4: Aryl Iodine Compounds

31.4.1 Product Subclass 1: Hypervalent Iodoarenes and Aryliodonium Salts

V. V. Zhdankin

31.4.1 Product Subclass 1: Hypervalent Iodoarenes and Aryliodonium Salts

31.4.1.1 Synthesis of Product Subclass 1

31.4.1.1.1 Synthesis by Oxidative Addition to Iodoarenes

31.4.1.1.1.1 Method 1: Iodylarenes by Oxidation of Iodoarenes

31.4.1.1.1.2 Method 2: (Difluoroiodo)arenes by Fluorination of Iodoarenes

31.4.1.1.1.2.1 Variation 1: Fluorination by Powerful Fluorinating Reagents

31.4.1.1.1.2.2 Variation 2: Electrochemical Fluorination

31.4.1.1.1.3 Method 3: (Dichloroiodo)arenes by Chlorination of Iodoarenes

31.4.1.1.1.4 Method 4: (Diacyloxyiodo)arenes by the Oxidation of Iodoarenes in the Presence of a Carboxylic Acid

31.4.1.1.1.5 Method 5: Benziodazoles by Oxidation of 2-Iodobenzamides

31.4.1.1.2 Synthesis by Ligand Exchange of Hypervalent Iodine Compounds

31.4.1.1.2.1 Method 1: Aryliodine(V) Carboxylates from Iodylarenes

31.4.1.1.2.2 Method 2: (Diacyloxyiodo)arenes from (Diacetoxyiodo)benzene by Ligand Exchange with a Carboxylic Acid

31.4.1.1.2.3 Method 3: Aryliodine(III) Peroxides by Exchange with tert-Butyl Hydroperoxide

31.4.1.1.2.4 Method 4: Aryliodine(III) Sulfonates from Arenes

31.4.1.1.2.4.1 Variation 1: [Hydroxy(organosulfonyloxy)iodo]arenes from (Diacetoxyiodo)arenes

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