The chemistry of reactive intermediates is central to a modern mechanistic and quantitative understanding of organic chemistry. Moreover, it underlies a significant portion of modern synthetic chemistry and is integral to a molecular view of biological chemistry. Reviews in Reactive Intermediate Chemistry presents an up-to-date, authoritative guide to this fundamental topic. Although it follows Reactive Intermediate Chemistry by the same authors, it serves as a free-standing resource for the entire chemical and biochemical community. The book includes: Relevant, practical applications Coverage of such topics as mass spectrometry methods, reactive intermediates in interstellar medium, quantum mechanical tunnelling, solvent effects, reactive intermediates in biochemical processes, and excited state surfaces Discussions of emerging areas, particularly those involving dynamics and theories Concluding sections identifying key directions for future research are provided at the end of each chapter

Most reactions in organic chemistry do not proceed in a single step but rather take several steps to yield the desired product. In the course of these multi-step reaction sequences, short-lived intermediates can be generated that quickly convert into other intermediates, reactants, products or side products. As these intermediates are highly reactive, they cannot usually be isolated, but their existence and structure can be proved by theoretical and experimental methods. Using the information obtained, researchers can better understand the underlying reaction mechanism of a certain organic transformation and thus develop novel strategies for efficient organic synthesis. The chapters are clearly structured and are arranged according to the type of intermediate, providing information on the formation, characterization, stereochemistry, stability, and reactivity of the intermediates. Additionally, representative examples and a problem section with different levels of difficulty are included for self-testing the newly acquired knowledge. By providing a deeper understanding of the underlying concepts, this is a musthave reference for PhD and Master Students in organic chemistry, as well as a valuable source of information for chemists in academia and industry working in the field. It is also ideal as primary or supplementary reading for courses on organic chemistry, physical organic chemistry or analytical chemistry.

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.

Organic Chemistry: A Series of Monographs, Volume 26: Organic Reactive Intermediates focuses on the study of reactive intermediates. This book discusses the methods of formation and investigation, factors affecting the stability, and reactions of the intermediate. Other topics include the formation and reaction of free radicals; kinetic aspects of free-radical chain reactions; electronic states and structures of carbenes; and formation of transient carbenes and carbenoids in solution. The intermediacy of nitrenes in reactions; electronic structure and spectra; methods of investigating carbonium ions; and reactions of carbonium ions are also elaborated. This publication likewise covers the preparation of carbanions; factors affecting the stability of carbanions; reactions involving radical ions; and methods of investigating arynes. This volume serves as a textbook for the first graduate-level course, as well as a reference for industrial chemists interested in organic reaction mechanisms.

A wonderfully successful NATO Advanced Study Institute on "Sulfur-Centered Reactive Intermediates in Chemistry and Biology" was held 18-30 June, 1989, at the Hotel Villa del Mare in Maratea, Italy. Despite the beautiful setting with mountains behind us and over looking the clear blue Mediterranean Sea under a cloudless sky (and with a private beach available), the lectures were extremely well attended. While some credit can go to the seriousness of the students, more must go to the calibre of speakers and the high quality of C. Chatgilialoglu, and Co-Director, Professor K. -D. their presentations. The Director, Dr. Asmus, are to be congratulated for putting together such an outstanding scientific program. Dr. Chatgilialoglu is also to be commended for arranging an equally stimulating social pro gram which included bus, train and boat trips to many local sites of interest. It was particularly fitting that a meeting on the chemistry and biochemistry of sulfur should be held in Italy since Italian chemists have made major contributions to our under standing of the organic chemistry of sulfur, including the chemistry of its reactive inter mediates. The early Italian interest in sulfur chemistry arose from the fact that Italy, or more specifically, Sicily, was a major world producer of sulfur prior to the development and exploitation of the Frasch process in Texas and Louisiana.

During the last two decades there has been considerable growth in the development of electrospray ionization mass spectrometry (ESI-MS) as a practical method in the study of reaction mechanisms. This method allows the interception and characterization of key intermediates, either as transient species or as protonated/deprotonated forms of neutral species by API-MS. The outstanding features and advantages of ESI-MS make it one of the most suitable tools for the fast screening of intermediates directly from solution, providing hitherto unavailable chemical information to organic chemists. This monograph provides an overview of the mechanisms involved in ESI-MS, the historical perspectives before looking further in-depth at specific reactions and intermediates. Written by researchers in the field, this book is an unique resource for the understanding of this cutting-edge technique.