Comprehensive Chirality - Hardcover

Hisashi Yamamoto

Hardcover

ISBN 10: 0080951678 ISBN 13: 9780080951676

Publisher: Elsevier Science, 2012

Synopsis

Although many books exist on the subject of chiral chemistry, they only briefly cover chiral synthesis and analysis as a minor part of a larger work, to date there are none that pull together the background information and latest advances in one comprehensive reference work. Comprehensive Chirality provides a complete overview of the field, and includes chiral research relevant to synthesis, analytic chemistry, catalysis, and pharmaceuticals. The individual chapters in each of the 9 volumes provide an in depth review and collection of references on definition, technology, applications and a guide/links to the related literature. Whether in an Academic or Corporate setting, these chapters will form an invaluable resource for advanced students/researchers new to an area and those who need further background or answers to a particular problem, particularly in the development of drugs.

• Chirality research today is a central theme in chemistry and biology and is growing in importance across a number of disciplinary boundaries. These studies do not always share a unique identifying factor or subject themselves to clear and concise definitions. This work unites the different areas of research and allows anyone working or researching in chiral chemistry to navigate through the most essential concepts with ease, saving them time and vastly improving their understanding.


•  The field of chirality counts several journals that are directly and indirectly concerned with the field. There is no reference work that encompasses the entire field and unites the different areas of research through deep foundational reviews. Comprehensive Chirality fills this vacuum, and can be considered the definitive work. It will help users apply context to the diverse journal literature offering and aid them in identifying areas for further research and/or for solving problems.


• Chief Editors, Hisashi Yamamoto (University of Chicago) and Erick Carreira (ETH Zürich) have assembled an impressive, world-class team of Volume Editors and Contributing Authors. Each chapter has been painstakingly reviewed and checked for consistent high quality. The result is an authoritative overview which ties the literature together and provides the user with a reliable background information and citation resource.

About this title

Review:

A complete overview of the chiral field including research relevant to synthesis, analytic chemistry, catalysis and pharmaceuticals

About the Author:

Chemists' ability to perform syntheses on a routine basis is due in large part to the development of new methods for synthesizing organic molecules which would have been impossible just a few decades ago. The availability of such new methods of synthesis has increased not only the range of structures which can be assembled but also the ease and economy of synthesis. During the past 30 years of his research, Professor Hisashi Yamamoto has had a tremendous impact on the field of organic chemistry through his reports of dramatic new advances in organic synthesis. Yamamoto's publications are numerous (over 450), and almost every one of them has provided an innovative new development or idea. Applications of this original and versatile chemistry have allowed him and other scientists to realize truly efficient syntheses of organic molecules of both theoretical and practical importance.

Hisashi Yamamoto has uncovered novel aspects of Lewis and Brønsted acid catalysts in selective organic synthesis. During his career he has discovered a wide variety of powerful new synthetic reactions, reagents, and catalysts based on acid catalysis chemistry. Through his dedicated efforts, Lewis and Brønsted acid are now recognized as major tools in the synthesis of both simple and complex organic molecules. Among Yamamoto's many superb contributions the following are especially worthy of mention.

His research in the area of organoaluminum chemistry has had a great impact on synthetic organic chemistry. The strong Lewis acidity of organoaluminum compounds appears to account for their strong tendency to form a stable 1:1 complex. Thus, the coordination of molecules invariably causes a change of reactivity, and the coordinated group may be activated or deactivated depending upon the type of reaction. Furthermore, with coordination of organic molecules an auxiliary bond can become coupled to the reagent and promote the desired reaction. In short, the reagents make a combined Lewis acid - Lewis base attack on a substrate with less activation energy, a field opened by Yamamoto's early and highly original studies. His aluminum amide reagents for epoxide rearrangement, biogenetic-type terpene synthesis, and the Beckmann rearrangement-alkylation reaction sequence are notable examples.

He was intrigued by the chemistry of the carbonyl compound-Lewis acid complex and introduced the unusually bulky organoaluminum reagents, methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) and aluminum tris(2,6-diphenylphenoxide) (ATPH). These reagents were successfully utilized for the selective alkylation of cyclic ketones and aldehydes to generate equatorial alcohol and an anti-Cram type product, respectively, for trans- and cis-selective Claisen rearrangement, for regioselective Diels-Alder reaction, and for epoxide-aldehyde rearrangement. The ATPH - aromatic carbonyl complex reacts with nucleophiles selectively at the para-position of the aromatic ring to generate cyclohexadiene derivatives.

After these pioneering researches in Lewis acid chemistry, Yamamoto has become aware of the vast importance of chiral Lewis acids in modern asymmetric synthesis. In 1985, he first introduced binaphthol as a key ligand for chiral Lewis acid catalysts. This work was the forerunner of a vast quantity of present-day research on the binaththol based chiral Lewis acid catalyst. Based on his knowledge of organoaluminum chemistry, he designed a new and powerful organoaluminum catalyst for asymmetric hetero-Diels-Alder reaction. It was his Brønsted acid-Lewis acid combined system, however, which gave him a unique opportunity for the most efficient asymmetric Lewis acid catalyst for Diels-Alder reaction. A similar concept was employed for his catalytic asymmetric protonation under acidic conditions, which now creates a long sought proton induced asymmetric polyene cyclization.

His discovery of tartaric acid based catalyst (CAB catalyst) and amino acid based catalyst led to the first enantioselective Diels-Alder reaction of a broad range of dienes and dienophiles. The same catalyst was shown to be the first highly efficient catalyst for asymmetric aldol and ene type reactions. The reaction is simple, exceedingly stereoselective, and environmentally friendly.

Direct condensation of carboxylic acids by alcohols or amines is the most important transformation of organic synthesis. Yamamoto found Lewis acid catalyst could play an important role for such esterification and amidation processes. For example, his new hafnium catalyzed esterification and boron catalyzed amidation are now becoming increasingly important to the chemical industry.

More recently, he has developed new asymmetric oxidation processes based on an acid catalysis concept. His nitroso chemistry offers an entirely new access to selective organic synthesis and provides catalytic enantioselective reaction to introduce oxygen and/or nitrogen into the molecule. His pyridine based nitroso- and azo-hetero-Diels-Alder provides powerful tool for asymmetric synthesis. He also recently reported asymmetric epoxidation of homoallylic alcohols based on new vanadium catalyst, one of the most difficult asymmetric oxidations to date.

After moving to Chicago, he proposed the use of 8-hydroxyquinole based chiral Lewis acid catalysis. The catalyst is designed as a rigid metal complex of cis-b-configuation. The reagent turned out to be a brand-new "privileged ligand" for asymmetric synthesis. Catalytic asymmetric pinacol coupling, NH reaction, Mukaiyama-Michael addition, and Pudovik reactions are now able to proceed with complete enantioselectivities.

His laboratory is also noted for its introduction of metal reagents that allow highly selective SN2 cross coupling with carbonyl and allylic electrophiles. Allylic organobarium reagent, so-called "Yamamoto's reagent", reacts with a variety of electrophiles selectively at less substituted termini with complete stereospecificity, resolving a long-standing problem in terpene synthesis.

About this edition

• Publisher: Elsevier Science
• Publication date: 2012
• ISBN 10: 0080951678
• ISBN 13: 9780080951676
• Binding: Hardcover
• Number of pages: 250
• Editor: Hisashi Yamamoto, Erick M Carreira