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 45b: Aromatic Ring Assemblies, Polycyclic Aromatic Hydrocarbons, and Conjugated Polyenes

Preface

Table of Contents

45.13 Product Class 13: Biaryls

D. A. Black and K. Fagnou

45.14 Product Class 14: Arylalkanes

D. A. Black and K. Fagnou

45.15 Product Class 15: Poly(phenylenes)

M. Abe and T. Yamamoto

45.16 Product Class 16: Poly(p-phenylenevinylenes)

L. Pu

45.17 Product Class 17: Poly(xylylenes)

T. Itoh

Product Class 18: Polystyrenes

F. Aldabbagh and O. Gibbons

45.19 Product Class 19: Naphthalenes, Anthracenes, 9H-Fluorenes, and Other Acenes

S. Toyota and T. Iwanaga

45.20 Product Class 20: Cyclobutabenzenes, Biphenylenes, and [N]Phenylenes

S. Toyota

45.21 Product Class 21: Phenanthrenes, Helicenes, and Other Angular Acenes

I. G. Stará and I. Starý

45.22 Product Class 22: Pyrenes, Circulenes, and Other Condensed Acenes

C.-S. Chang and Y.-T. Wu

45.23 Product Class 23: Annulated Polycyclic Aromatic Hydrocarbons

W.-C. Lin and Y.-T. Wu

45.24 Product Class 24: Pentalenes, s-Indacenes, as-Indacenes, Azulenes, and Heptalenes, and Their Benzo Derivatives

K. Abou-Hadeed and H.-J. Hansen

45.25 Product Class 25: Extended Polyaromatic Hydrocarbons: Graphite, Fullerene, and Carbon Nanotube Substructures

I. G. Stará and I. Starý

45.26 Product Class 26: Triphenylenes, Tetraphenylenes, and Related Compounds

S. R. Waldvogel and N. Welschoff

45.27 Product Class 27: Calixarenes

T. Haino and H. Iwamoto

45.28 Product Class 28: Mononuclear Cyclophanes

T. Shinmyozu and M. Shibahara

45.29 Product Class 29: Polynuclear Cyclophanes

Y. Tobe and T. Takeda

45.30 Product Class 30: Conjugated Polyenes, Including Cyclic Polyenes That Are Not Fully Conjugated

S. Koo

45.31 Product Class 31: Macromolecular Conjugated Polyenes

T. Masuda, M. Shiotsuki, and F. Sanda

Keyword Index

Author Index

Abbreviations

Table of Contents

45.13 Product Class 13: Biaryls

D. A. Black and K. Fagnou

45.13 Product Class 13: Biaryls

45.13.1 Synthesis of Product Class 13

45.13.1.1 Synthesis Using Copper Catalysis

45.13.1.1.1 Method 1: The Ullmann Reaction

45.13.1.1.2 Method 2: Cross-Coupling Reactions

45.13.1.1.2.1 Variation 1: Using Boronic Acids

45.13.1.1.2.2 Variation 2: Using Organotin Reagents

45.13.1.2 The Suzuki Cross-Coupling Reaction

45.13.1.2.1 Method 1: Aryl Iodides in Suzuki Cross-Coupling Reactions

45.13.1.2.2 Method 2: Aryl Bromides in Suzuki Cross-Coupling Reactions

45.13.1.2.3 Method 3: Aryl Chlorides in Suzuki Cross-Coupling Reactions

45.13.1.2.4 Method 4: Aryl 4-Toluenesulfonates and Trifluoromethanesulfonates in Suzuki Cross-Coupling Reactions

45.13.1.2.5 Method 5: Diazonium Salts in Suzuki Cross-Coupling Reactions

45.13.1.2.6 Method 6: Synthesis of Hindered Biaryls Using the Suzuki Cross-Coupling Reaction

45.13.1.2.7 Method 7: Synthesis of Oligoaromatics Using the Suzuki Cross-Coupling Reaction

45.13.1.3 The Stille Cross-Coupling Reaction

45.13.1.3.1 Method 1: Aryl Iodides in Stille Cross-Coupling Reactions

45.13.1.3.2 Method 2: Aryl Bromides in Stille Cross-Coupling Reactions

45.13.1.3.3 Method 3: Aryl Chlorides in Stille Cross-Coupling Reactions

45.13.1.3.4 Method 4: Aryl Trifluoromethanesulfonates in Stille Cross-Coupling Reactions

45.13.1.3.5 Method 5: Synthesis of Hindered Biaryls Using the Stille Cross-Coupling Reaction

45.13.1.4 The Negishi Cross-Coupling Reaction

45.13.1.4.1 Method 1: Aryl Iodides in Negishi Cross-Coupling Reactions

45.13.1.4.2 Method 2: Aryl Bromides in Negishi Cross-Coupling Reactions

45.13.1.4.3 Method 3: Aryl Chlorides in Negishi Cross-Coupling Reactions

45.13.1.4.4 Method 4: Aryl Trifluoromethanesulfonates in Negishi Cross-Coupling Reactions

45.13.1.4.5 Method 5: Synthesis of Hindered Biaryls Using the Negishi Cross-Coupling Reaction

45.13.1.5 The Hiyama Cross-Coupling Reaction

45.13.1.5.1 Method 1: Aryl Iodides in Hiyama Cross-Coupling Reactions

45.13.1.5.2 Method 2: Aryl Bromides in Hiyama Cross-Coupling Reactions

45.13.1.5.3 Method 3: Aryl Chlorides in Hiyama Cross-Coupling Reactions

45.13.1.5.4 Method 4: Aryl Trifluoromethanesulfonates in Hiyama Cross-Coupling Reactions

45.13.1.5.5 Method 5: Synthesis of Oligoaromatics Using the Hiyama Cross-Coupling Reaction

45.13.1.6 The Kumada–Corriu Cross-Coupling Reaction

45.13.1.6.1 Method 1: Aryl Iodides in Kumada–Corriu Cross-Coupling Reactions

45.13.1.6.2 Method 2: Aryl Bromides in Kumada–Corriu Cross-Coupling Reactions

45.13.1.6.3 Method 3: Aryl Chlorides in Kumada–Corriu Cross-Coupling Reactions

45.13.1.6.4 Method 4: Aryl Trifluoromethanesulfonates and Arenesulfonates in Kumada–Corriu Cross-Coupling Reactions

45.13.1.6.5 Method 5: Synthesis of Hindered Biaryls Using the Kumada–Corriu Cross-Coupling Reaction

45.13.1.6.6 Method 6: Synthesis of Oligoaromatics Using the Kumada–Corriu Coupling Reaction

45.13.1.7 Direct Arylation

45.13.1.7.1 Method 1: Intramolecular Direct Arylation

45.13.1.7.2 Method 2: Intermolecular Direct Arylation

45.13.1.7.2.1 Variation 1: In the Presence of Directing Groups

45.13.1.7.2.2 Variation 2: Without Directing Groups

45.13.1.7.3 Method 3: Palladium-Catalyzed Domino/Cascade Reactions Involving Direct Arylation

45.14 Product Class 14: Arylalkanes

D. A. Black and K. Fagnou

45.14 Product Class 14: Arylalkanes

45.14.1 Synthesis of Product Class 14

45.14.1.1 Method 1: Friedel–Crafts Alkylation

45.14.1.1.1 Variation 1: Using Alkyl Halides

45.14.1.1.2 Variation 2: Using Alkenes

45.14.1.1.3 Variation 3: Using Alcohols

45.14.1.1.4 Variation 4: Using Esters

45.14.1.1.5 Variation 5: Asymmetric Friedel–Crafts Alkylation

45.14.1.2 Method 2: Alkylation of Aromatic Ketones with Alkenes by C-H Activation

45.14.1.3 Method 3: Alkylation via Transition-Metal-Catalyzed Cross-Coupling Reactions with Alkyl Electrophiles

45.14.1.3.1 Variation 1: Kumada Cross-Coupling Reaction

45.14.1.3.2 Variation 2: Suzuki Cross-Coupling Reaction

45.14.1.3.3 Variation 3: Negishi Cross-Coupling Reaction

45.14.1.3.4 Variation 4: Stille Cross-Coupling Reaction

45.14.1.3.5 Variation 5: Hiyama Cross-Coupling Reaction

45.14.1.4 Method 4: Alkylation via Transition-Metal-Catalyzed Cross-Coupling Reactions with Alkyl Nucleophiles

45.14.1.4.1 Variation 1: Kumada Cross-Coupling Reaction

45.14.1.4.2 Variation 2: Suzuki Cross-Coupling Reaction

45.14.1.4.3 Variation 3: Negishi Cross-Coupling Reaction

45.14.1.4.4 Variation 4: Hiyama Cross-Coupling Reaction

45.15 Product Class 15: Poly(phenylenes)

M. Abe and T. Yamamoto

45.15 Product Class 15: Poly(phenylenes)

45.15.1 Product Subclass 1: Linear Poly(phenylenes)

45.15.1.1 Synthesis of Product Subclass 1

45.15.1.1.1 Method 1: Kovacic Procedure

45.15.1.1.2 Method 2: Dehalogenative Polycondensation Reactions of Disubstituted Benzenes Using Nickel(0) Complexes

45.15.1.1.2.1 Variation 1: Using Bis(η⁴-cycloocta-1,5-diene)nickel(0)

45.15.1.1.2.2 Variation 2: Using a Nickel Complex as the Catalyst and Zinc as the Reducing Reagent

45.15.1.1.3 Method 3: Grignard Coupling Reactions

45.15.1.1.4 Method 4: Suzuki Coupling Reactions

45.15.1.1.4.1 Variation 1: AB-Type Approach

45.15.1.1.4.2 Variation 2: AA/BB-Type Approach

45.15.1.1.5 Method 5: Stille Coupling Reactions

45.15.1.1.6 Method 6: Reactions Utilizing Intermediate Polymers

45.15.1.1.6.1 Variation 1: Aromatization by Decarboxylation of Soluble Precursor Polymers

45.15.1.1.6.2 Variation 2: Decarboxylation of a Precursor with a Poly(p-phenylene) Backbone

45.15.1.1.7 Method 7: Diels–Alder Polycondensations

45.15.2 Product Subclass 2: Macrocyclic Poly(phenylenes)

45.15.2.1 Synthesis of Product Subclass 2

45.15.2.1.1 Method 1: Reductive Coupling Reactions

45.15.2.1.2 Method 2: Suzuki Coupling Reactions

45.15.3 Product Subclass 3: Dendritic Poly(phenylenes)

45.15.3.1 Synthesis of Product Subclass 3

45.15.3.1.1 Method 1: Suzuki Coupling Reactions

45.15.3.1.2 Method 2: Diels–Alder Cycloaddition Reactions

45.16 Product Class 16: Poly(p-phenylenevinylenes)

L. Pu

45.16 Product Class 16: Poly(p-phenylenevinylenes)

45.16.1 Product Subclass 1: Unsubstituted Poly(p-phenylenevinylenes)

45.16.1.1 Synthesis of Product Subclass 1

45.16.1.1.1 Method 1: Polymerization of Sulfonium Salts

45.16.1.1.2 Method 2: Polymerization of Dithiocarbonates

45.16.1.1.3 Method 3: Polymerization of Dithiocarbamates

45.16.1.1.4 Method 4: Polymerization of Sulfinyl Compounds

45.16.1.1.5 Method 5: Ring-Opening Metathesis Polymerization

45.16.2 Product Subclass 2: Substituted, Soluble Poly(p-phenylenevinylenes)

45.16.2.1 Synthesis of Product Subclass 2

45.16.2.1.1 Method 1: Polymerization of Sulfonium Salts

45.16.2.1.2 Method 2: The Gilch Method

45.16.2.1.3 Method 3: Polymerization of Dithiocarbamates

45.16.2.1.4 Method 4: Wittig Reactions

45.16.2.1.5 Method 5: Horner Reactions

45.16.2.1.6 Method 6: Heck Coupling

45.16.2.1.7 Method 7: Stille Coupling

45.16.2.1.8 Method 8: Acyclic Diene Metathesis Polymerization

45.16.2.1.9 Method 9: Ring-Opening Metathesis Polymerization

45.16.2.1.10 Method 10: Polymerization of (Dichloromethyl)aryls

45.16.2.1.11 Method 11: McMurry Reaction

45.16.2.1.12 Method 12: Knoevenagel Condensation

45.17 Product Class 17: Poly(xylylenes)

T. Itoh

45.17 Product Class 17: Poly(xylylenes)

45.17.1 Product Subclass 1: Poly(p-xylylenes)

45.17.1.1 Synthesis of Product Subclass 1

45.17.1.1.1 Method 1: Wurtz–Fittig Dehalogenation of 1,4-Bis(halomethyl)arenes in the Presence of a Metal

45.17.1.1.2 Method 2: Friedel–Crafts Coupling of Benzene with 1,2-Dihaloethanes, or of (2-Haloethyl)benzenes

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