Synthesis of Biaryls
- Ivica Cepanec, Director of Research & Development Department BELUPO Pharmaceuticals Inc., Zagreb, CROATIA
Organic chemistry is one of the most rapidly growing sciences. There is a wide variety of applications of organic compounds, for instance, pharmaceutically active substances, agrochemicals, optoelectronics, etc. Within this group there are hundereds and thousands of new compounds synthesized or isolated from natural sources. Such important organic chemistry developments are accompanied by the profound break-through of new reactions, increasingly efficient methodologies, reagents and catalysts. The chemistry of biaryls is one of the most interesting fields in organic chemistry, this book looks at these reactions both new and old.
Synthesis of Biaryls presents the description of a given method for the synthesis of biaryls: short introduction, reaction mechanism, application, representative synthetic procedures, conclusion and literature references. This book will be of interest to organic chemists in industry and academia.
All research chemists, undergraduate, postgraduate and practitioners in the field of organic chemistry
- Published: July 2004
- Imprint: ELSEVIER
- ISBN: 978-0-08-044412-3
"The writing and preparation of this book has clearly been a labor of love for Dr. Cepanec. He has provided exhaustive coverage of the old and the new, critically analyzed and compared the methods, provided data on best conditions for first attempts, given mechanistic insight as it relates to synthetic optimization, and listed selected synthetic procedures, some from direct experience, for use in the lab. The text is clear, the equations are instructive, with more than the normal details of conditions, and the index is substantial and carefully constructed. The field of aryl-aryl coupling is omnipresent in chemical synthesis and is therefore required knowledge for the modern practicing chemist. This volume not only provides that knowledge and examples of its applications, it also fosters an appreciation of biaryl synthesis."
Victor Snieckus, Queen's University
Table of Contents1. INTRODUCTION.
Aryl-aryl bond forming reactions. The importance of biaryls. Structure of biaryls. Atropisomerism.
2. CLASSICAL METHODS FOR SYNTHESIS OF BIARYLS.
The Ullmann and Related reactions. The Gomberg-Bachmann-Hey reaction. The Pschorr cyclization. The Gatterman synthesis of biaryls. Arylation of arenes with diaroyl peroxides. Selected synthetic procedures.
3. COUPLING REACTIONS OF ARYL HALIDES AND SULFONATES WITH METAL COMPLEXES AND ACTIVE METALS.
Reaction mechanism. biaryls catalysed by nickel complexes. Homo-coupling reactions of aryl halides to biaryls catalysed by palladium complexes. Cross-coupling reactions of aryl halides to biaryls. catalysed by nickel-and palladium-complexes. Homo-coupling reactions of aryl halides to biaryls mediated by copper(I) salts. Homo-coupling reactions of aryl halides to biaryls promoted by active metals. Selected synthetic procedures.
4. CROSS-COUPLING REACTIONS OF ARYLMETALLIC REAGENTS WITH ARYL HALIDES AND ARYL SULFONATES.
Reaction mechanism. Cross-coupling reactions of aryl halides and triflates with aryllithium and Grignard reagents, the Kharasch reaction. The Negishi reaction. The Stille reaction. Cross-coupling reactions of arylsilanes with aryl halides. Cross-coupling reaction of diarylmercurials with aryl halides. Cross-coupling reaction of arylcopper reagents with aryl halides. Cross-coupling reactions of miscellaneous arylmetallic: Mn, Ti, In and Ge reagents with aryl halides and sulfonates. Selected synthetic procedures.
5. THE SUZUKI-MIYAURA REACTION.
General survey of the Suzuki-Miyaura reaction. Methods for performing the Suzuki-Miyaurasynthesis of biaryls. Modern Suzuki-Miyaura reaction catalysts. Synthesis of arylboronic acids. Selected synthetic procedures.
6. SYNTHESIS OF BIARYLS AND POLYARYLS BY OXIDATIVE COUPLINGS OF ARENES.
Mechanisms of oxidative couplings of arenesto biaryls and polyaryls. Oxidative couplings of arenes to biaryls and polyaryls. Selected synthetic procedures.
7. MISCELLANEOUS METHODS FOR SYNTHESIS OF BIARYLS.
Free-radical arylations of arenes with arylhydrazines and arylboronic acids. Homo-coupling reactions of miscellaneous arylmetallic reagents to biaryls. The Meyers synthesis of biaryls and Related reactions. Diaryliodonium salts and other hypervalent iodine compounds in the synthesis of biaryls. Palladium-catalysed arylation of arenes with aryl halides and sulfonates. Synthesis of biaryls involving aryllead(IV) tricarboxylates.Synthesis of biaryls involving arylbismuth and arylantimony reagents. Synthesis of biaryls via benzidine rearrangement. Photochemical synthesis of biaryls. Other methods for synthesis of biaryls. Selected synthetic procedures.
8. SYNTHESIS OF AXIALLY CHIRAL BIARYLS.
Diastereoselective synthesis of biaryls. Enantioselective synthesis of biaryls.Selected synthetic procedures.