Examining the formation, transformation, and application of ion radicals in typical conditions of organic synthesis, Organic Ion Radicals: Chemistry and Applications explains the reactions and principles of ion radical chemistry. The author addresses methods of determining ion- radical mechanisms and controlling ion radical reactions, issues relating to ecology and biology, and inorganic participants in ion radical organic reactions. Applications discussed include the roles of ion radicals in biological systems and their uses in optoelectronics, organic metals, and the manufacture of paper.
Consolidating knowledge from a number of disciplines, Ion-Radical Organic Chemistry: Principles and Applications, Second Edition presents the recent changes that have occurred in the field since the publication of the first edition in 2003. This volume examines the formation, transformation, and application of ion-radicals in typical conditions of organic synthesis. Avoiding complex mathematics, the author explains the principles of ion-radical organic chemistry and presents an overview of organic ion-radical reactions. He reviews methods of determining ion-radical mechanisms and controlling ion-radical reactions. Wherever applicable, the text addresses issues relating to ecology and biomedical concerns as well as inorganic participants of the ion-radical organic reactions. After reviewing the nature of organic ion-radicals and their ground-state electronic structure, the book discusses their formation, the relationship between electronic structure and reactivity, mechanism and regulation of reactions, stereochemical aspects, synthetic opportunities, and practical applications. Additional topics include electronic and opto-electronic devices, organic magnets and conductors, lubricants, other materials, and reactions of industrial or biomedical importance. The book concludes by providing an outlook on possible future development in this field. Researchers and practitioners engaged in active work on synthetic or mechanistic organic chemistry and its practical applications will find this text to be invaluable in both its scope and its depth.
Free radicals constitute the most frequently used class of reaction intermediates in organic chemistry. This study describes the structure and reactivity of free radicals, and explores their role in both natural phenomena and in the design of new reaction pathways.
Covers the most advanced computational and experimental methods for studying carbon-centered radical intermediates With its focus on the chemistry of carbon-centered radicals and radical cations, this book helps readers fully exploit the synthetic utility of these intermediates in order to prepare fine chemicals and pharmaceutical products. Moreover, it helps readers better understand their role in complex atmospheric reactions and biological systems. Thoroughly up to date, the book highlights the most advanced computational and experimental methods available for studying and using these critically important intermediates. Carbon-Centered Free Radicals and Radical Cations begins with a short history of the field of free radical chemistry, and then covers: A discussion of the relevant theory Mechanistic chemistry, with an emphasis on synthetic utility Molecular structure and mechanism, focusing on computational methods Spectroscopic investigations of radical structure and kinetics, including demonstrations of spin chemistry techniques such as CIDNP and magnetic field effects Free radical chemistry in macromolecules Each chapter, written by one or more leading experts, explains difficult concepts clearly and concisely, with references to facilitate further investigation of individual topics. The authors were selected in order to provide insight into a broad range of topics, including small molecule synthesis, polymer degradation, computational chemistry as well as highly detailed experimental work in the solid, liquid, and gaseous states. This volume is essential for students or researchers interested in building their understanding of the role of carbon-centered radical intermediates in complex systems and how they may be used to develop a broad range of useful products.
Comprehensive coverage of radical reactive intermediates in nucleic acid chemistry and biochemistry The Wiley Series on Reactive Intermediates in Chemistry and Biology investigates reactive intermediates from the broadest possible range of disciplines. The contributions in each volume offer readers fresh insights into the latest findings, emerging applications, and ongoing research in the field from a diverse perspective. The chemistry and biochemistry of reactive intermediates is central to organic chemistry and biochemistry, and underlies a significant portion of modern synthetic chemistry. Radical and Radical Ion Reactivity in Nucleic Acid Chemistry provides the only comprehensive review of the chemistry and biochemistry of nucleic acid radical intermediates. With contributions by world leaders in the field, the text covers a broad range of topics, including: A discussion of the relevant theory Ionization of DNA Nucleic acid sugar radicals Halopyrimidines Oxidative, reductive, and low energy electron transfer Electron affinity sensitizers Photochemical generative of reactive oxygen species Reactive nitrogen species Enediyne rearrangements Phenoxyl radicals A unique compilation on the cutting edge of our understanding, Radical and Radical Ion Reactivity in Nucleic Acid Chemistry provides an unparalleled resource to student and professional researchers in such fields as organic chemistry, biochemistry, molecular biology, and physical chemistry, as well as the industries associated with these disciplines.
Considering the challenge of sustainability facing our society in the coming decades, catalysis is without any doubt a research area of major importance. In this regard, asymmetric organocatalysis, now considered a pillar of green chemistry, deserves particular attention. The first chapter of this volume examines the topic of asymmetric organocatalysis in light of radical chemistry. Recent important progress in this field has been attained by promoting the formation and harnessing the high reactivity of open-shell intermediates. Merging organocatalysis with radical chemistry has been the key to solving some longstanding bottlenecks, and has also significantly contributed to reinforcing the key role of organocatalysis in asymmetric catalysis. This chapter presents the most significant developments in this area, with a particular focus on asymmetric SOMO- and photoredox-organocatalyzed transformations. Chapter 2 focuses on quaternary ammonium salts (R4N+X-), especially chiral derivatives, and their behavior as unique catalysts in organocatalysis. Forming chiral ion-pairs capable of promoting asymmetric reactions, they also operate as unique "transporters involved in phase transfer catalytic processes between liquid–liquid or liquid–solid systems. Furthermore, they offer unique opportunities when forming cooperative ion-paired entities R4N+X-, allowing a synergistic implication of the counter-ion X- either as Brønsted bases or Lewis bases. Specific design of such chiral catalysts in modern chemistry and better insight into their mode of activation facilitates efficient and unprecedented chemical transformations. This chapter provides an overview of the use of chiral quaternary ammonium salts in organocatalysis, emphasizing both general mechanistic aspects and the scope of this approach. - Presents the most significant developments with a particular focus on asymmetric SOMO- and photoredox-organocatalyzed transformations - Givies a larger overview of chiral ammonium salts in organocatalysis rather than a specific review dedicated to specialists in this area - Affords a historical evolution of this field of research
Free radical reactions have become increasingly important and a very attractive tool in organic synthesis in the last two decades, due to their powerful, selective, specific, and mild reaction abilities. Advanced Free Radical Reactions for Organic Synthesis reviews information on all types of practical radical reactions, e.g. cyclizations, additions, hydrogen-atom abstractions, decarboxylation reactions. The book usefully provides experimental details for the most important reactions as well as numerous references to the original literature. By covering both the fundamentals and synthetic applications it is therefore suitable for both new and experienced researchers, chemists, biochemists, natural product chemists and graduate students. This title is the definitive guide to radical chemistry for all scientists. Introduces and reviews the use of radicals to perform synthetic transformations Practical details are provided for the most important methods Numerous references to the original literature
Presentation is clear and instructive: students will learn to recognize that many of the reactions in organic chemistry are closely related and not independent facts needing unrelated memorization. The book emphasizes that derivation of a mechanism is not a theoretical procedure, but a means of applying knowledge of other similar reactions and reaction conditions to the new reaction. - Brief summaries of required basic knowledge of organic structure, bonding, stereochemistry, resonance, tautomerism, and molecular orbital theory - Definitions of essential terms - Typing and classification of reactions - Hints (rules) for deriving the most likely mechanism for any reaction
Find an easier way to learn organic chemistry with Arrow-Pushing in Organic Chemistry: An Easy Approach to Understanding Reaction Mechanisms, a book that uses the arrow-pushing strategy to reduce this notoriously challenging topic to the study of interactions between organic acids and bases. Understand the fundamental reaction mechanisms relevant to organic chemistry, beginning with Sn2 reactions and progressing to Sn1 reactions and other reaction types. The problem sets in this book, an excellent supplemental text, emphasize the important aspects of each chapter and will reinforce the key ideas without requiring memorization.
Free radical initiators–chemical molecules which easily decompose into free radicals–serve as reactive intermediates in synthetic methodologies such as organic and polymer synthesis as well as in technological processes, oligomerization, network formation, and kinetic research. The Handbook of Free Radical Initiators presents an up-to-date account of the physicochemical data on radical initiators and reactions of radical generation. Individual chapters include: Dialkyl Peroxides and Hydroperoxides Diacyl Peroxides, Peresters, and Organic Polyoxides Azo-Compounds Bimolecular Reactions of Free Radical Generation by Ozone, Dioxygen, Hydroperoxides, and Haloid Molecules Free Radical Abstraction Reactions Free Radical Addition Reactions Free Radical Recombination and Disproportoination Reactions Professionals and academic researchers in chemical engineering, pharmaceuticals, biotechnology, plastics, and rubbers will find the Handbook of Free Radical Initiators to be a distinguished, vital resource.
