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Reactive Intermediate Chemistry presents a detailed and timely examination of key intermediates central to the mechanisms of numerous organic chemical transformations. Spectroscopy, kinetics, and computational studies are integrated in chapters dealing with the chemistry of carbocations, carbanions, radicals, radical ions, carbenes, nitrenes, arynes, nitrenium ions, diradicals, etc. Nanosecond, picosecond, and femtosecond kinetic realms are explored, and applications of current dynamics and electronic structure calculations are examined. Reactive Intermediate Chemistry provides a deeper understanding of contemporary physical organic chemistry, and will assist chemists in the design of new reactions for the efficient synthesis of pharmaceuticals, fine chemicals, and agricultural products. Among its features, this authoritative volume is: Edited and authored by world-renowned leaders in physical organic chemistry. Ideal for use as a primary or supplemental graduate textbook for courses in mechanistic organic chemistry or physical chemistry. Enhanced by supplemental reading lists and summary overviews in each chapter.
PERSPECTIVES ON STRUCTURE AND MECHANISM IN ORGANIC CHEMISTRY “Beyond the basics” physical organic chemistry textbook, written for advanced undergraduates and beginning graduate students Based on the author’s first-hand classroom experience, Perspectives on Structure and Mechanism in Organic Chemistry uses complementary conceptual models to give new perspectives on the structures and reactions of organic compounds, with the overarching goal of helping students think beyond the simple models of introductory organic chemistry courses. Through this approach, the text better prepares readers to develop new ideas in the future. In the 3rd Edition, the author thoroughly updates the topics covered and reorders the contents to introduce computational chemistry earlier and to provide a more natural flow of topics, proceeding from substitution, to elimination, to addition. About 20% of the 438 problems have been either replaced or updated, with answers available in the companion solutions manual. To remind students of the human aspect of science, the text uses the names of investigators throughout the text and references material to original (or accessible secondary or tertiary) literature as a guide for students interested in further reading. Sample topics covered in Perspectives on Structure and Mechanism in Organic Chemistry include: Fundamental concepts of organic chemistry, covering atoms and molecules, heats of formation and reaction, bonding models, and double bonds Density functional theory, quantum theory of atoms in molecules, Marcus Theory, and molecular simulations Asymmetric induction in nucleophilic additions to carbonyl compounds and dynamic effects on reaction pathways Reactive intermediates, covering reaction coordinate diagrams, radicals, carbenes, carbocations, and carbanions Methods of studying organic reactions, including applications of kinetics in studying reaction mechanisms and Arrhenius theory and transition state theory A comprehensive yet accessible reference on the subject, Perspectives on Structure and Mechanism in Organic Chemistry is an excellent learning resource for students of organic chemistry, medicine, and biochemistry. The text is ideal as a primary text for courses entitled Advanced Organic Chemistry at the upper undergraduate and graduate levels.
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This book provides the most up-to-date and comprehensive coverage of the structures and properties of polysaccharides, methods for their characterization, de novo synthesis, and modification, as well as advances in structure/function correlations. Many of these topics are summarized for the first time.A brief survey of polysaccharide structures is given highlighting the most significant advances in analytical and spectroscopic technology (NMR, MS, etc.). A chapter is devoted to glycan properties, including conformational aspects, rheological and compatibility characteristics, etc. There is a comprehensive overview of the de novo synthesis of carbohydrate polymers, the transformation of glycans into novel types of polymers, and the preparation of linear and branched polysaccharide analogues and conjugates with synthetic polymers via chemical and enzymatic approaches. The book also details the factors controlling the uniformity of substitutions in homogeneous and heterogeneous derivatization processes and the elucidation of the substitution patterns of partially modified polysaccharides, through combined spectroscopic and statistical methods.One of the important developments in the glycan field is based on the increasing demand for greater control of the functional properties of these biopolymers. The book provides a very extensive account of various types of modifications, including selective and non-selective chemical techniques, biological methods that facilitate alterations or specific functional groups and properties through the application of synthetic or degradative enzymes, and mutational or recombinant DNA techniques. The coverage extends to the control of glycan integrity and molecular weight through chemical enzymatic, physical or other methods. Electrochemical modification techniques are also discussed.A particularly up-to-date and comprehensive review is given of polysaccharide structure/property relations. Here, the effects of primary structural parameters (composition, molecular size, branching, polyelectrolyte character and non-carbohydrate substituents) are discussed, as are factors which affect glycan solubility, viscosity and gel-forming capacity. Also included are the phenomena resulting from the interactions of polysaccharides with solvents, salts, polyols, surfactants, synthetic and biological polymers. The impact of glycan structural parameters on various biological activities, such as immunological, anticoagulant, and antitumour properties, is surveyed.The book features a foreword by Dr. R.H. Marchessault, and contains almost 2,000 references to the state-of-the-art in the field, as well as an extensive subject index, over 40 tables, and 130 schemes and illustrations. It provides a wealth of valuable information for specialists in polysaccharides, biochemists, biotechnologists, enzymologists, microbiologists, organic chemists, polymer scientists, and others whose work involves these biopolymers.
This Volume covers the formation of carbon-carbon single-, double- and triple bonds by substitution and addition reactions as well as by various rearrangements. The formation of carbon-carbon multiple bonds by elimination and condensation procedures is fully documented. In addition the synthesis of carbon-hydrogen bonds principally by substitution and addition reactions is featured as is the preparation of a wide variety of carbon-centred anions, cations and radicals.
Rearrangement in ground and excited states, Volume 1 covers essays on the rearrangements of carbocations; gas-phase ion rearrangements; and rearrangements of carbenes and nitrenes. The book also includes essays on the free-radical rearrangements; hypothetical biradical pathways in thermal unimolecular rearrangements; and rearrangements in carbanions. Chemists and people involved in the study of rearrangements will find the book invaluable.