The Elucidation Of Mechanisms Of Multicentered Organic Reactions By The Use Of Kinetic Isotope Effects
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The Elucidation Of Mechanisms Of Multicentered Organic Reactions By The Use Of Kinetic Isotope Effects
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Author : William Shakespeare Morrison
language : en
Publisher:
Release Date : 1973
The Elucidation Of Mechanisms Of Multicentered Organic Reactions By The Use Of Kinetic Isotope Effects written by William Shakespeare Morrison and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1973 with Chemical kinetics categories.
Heavy Atom Kinetic Isotope Effects
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Author : Marvin J. Stern
language : en
Publisher:
Release Date : 1972
Heavy Atom Kinetic Isotope Effects written by Marvin J. Stern and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1972 with Chemical kinetics categories.
Investigations Of Structure And Mechanism In Organic Reactions Using Kinetic Isotope Effects
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Author : Matthew P. Meyer
language : en
Publisher:
Release Date : 2001
Investigations Of Structure And Mechanism In Organic Reactions Using Kinetic Isotope Effects written by Matthew P. Meyer and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2001 with categories.
Isotope Effects In Chemistry And Biology
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Author : Amnon Kohen
language : en
Publisher: CRC Press
Release Date : 2005-11-01
Isotope Effects In Chemistry And Biology written by Amnon Kohen and has been published by CRC Press this book supported file pdf, txt, epub, kindle and other format this book has been release on 2005-11-01 with Medical categories.
The field of isotope effects has expanded exponentially in the last decade, and researchers are finding isotopes increasingly useful in their studies. Bringing literature on the subject up to date, Isotope Effects in Chemistry and Biology covers current principles, methods, and a broad range of applications of isotope effects in the physical, biolo
Deuterium Kinetic Isotope Effects As Mechanistic Probes For Synthetically Useful Cyclic Hydrogen Transfers
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Author :
language : en
Publisher:
Release Date : 2016
Deuterium Kinetic Isotope Effects As Mechanistic Probes For Synthetically Useful Cyclic Hydrogen Transfers written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2016 with categories.
Hydrogen transfer reactions are among the most fundamental organic reactions. They are involved in nearly all enzyme-catalyzed reactions necessary for the sustenance of life, and they are often involved in key steps in synthetically useful reductions. Notable among synthetically useful reactions are the class of reactions known as C-H bond functionalization. It is surprising, then, that this most fundamental chemical event is so poorly understood. To address this knowledge gap, we have developed new experimental and computational approaches that allow interrogation of the core physical nature of cyclic hydrogen transfer reactions. In general, our laboratory utilizes kinetic isotope effects (KIEs) to probe chemical reactions. This technique involves accurately determining how replacement of atoms with their heavier isotopes affects the reaction rate (or product distribution). In order to extract the most insightful information from KIE studies, suitable experiments and measurement methods need to be well-designed and carefully executed. This dissertation is composed of four chapters. The first chapter serves as a general introduction that lays out the background of the mechanistic study of cyclic hydrogen transfer, the concepts of kinetic isotope effect and a concise review of traditional and new techniques that utilize KIEs to elucidate reaction mechanisms. The remaining chapters present three unique studies that culminate in a unified view of cyclic hydrogen transfers. Each study is designed to interrogate the key physical aspects of a synthetically useful and mechanistically interesting hydrogen transfer. The first study explores the Chugaev elimination, which is used to transform alcohols into alkenes in a typically regioselective manner. In this study, we have used a combination of intermolecular and intramolecular 2H KIE measurements to demonstrate that this reaction is dominated by quantum mechanical behavior even though it occurs at elevated temperatures. Comparison between the experimental and computational results imply that the observed KIEs are influenced by the location of the bottleneck (or transition state) which is found to be dependent on the isotopic substitution. Chapter 3 explores the Cope elimination, which can be used to install alkenes adjacent to an amine, demonstrated that seemingly simple cyclic hydrogen transfer reactions can proceed simultaneously via multiple mechanisms depending upon driving force and temperatures. Our approaches in the Cope and Chugaev eliminations were then utilized to explore an exciting new C-H functionalization reaction developed by DuBois. This study demonstrates that cyclic H-transfers mediated by a Ru-nitrene species are fundamentally similar to relatively simpler syn-b eliminations in terms of the involvement of quantum mechanical phenomena. The reaction models built with prototype reactions can be generalized to more complicated metal catalyzed reactions to facilitate a better understanding of the reaction in terms of both reactivity and selectivity.
Enzyme Mechanism From Isotope Effects
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Author : Paul F. Cook
language : en
Publisher: CRC Press
Release Date : 1991-09-20
Enzyme Mechanism From Isotope Effects written by Paul F. Cook and has been published by CRC Press this book supported file pdf, txt, epub, kindle and other format this book has been release on 1991-09-20 with Medical categories.
Isotope effects have become one of the most powerful tools available to the enzymologist for probing enzymic mechanisms. Enzyme Mechanism from Isotope Effects presents the basic theory underlying isotope effects, including the latest findings on proton tunneling and coupled atomic notions. Specific theoretical applications are emphasized in regard to the types of information that can be obtained using isotope effects. The book also examines recent theoretical treatments of the product dependence of deuterium isotope effects, multiple isotope effects and isotope effects on intermediate partitioning. Other topics include a complete discussion of methods for measuring isotope effects, including a detailed description of the use of the isotope ratio mass spectrometer to obtain isotope effects, and a review of the literature regarding mechanistic information obtained from isotope effects for individual classes of enzyme-catalyzed reactions. Enzyme Mechanism from Isotope Effects is an excellent reference source for investigators using isotope effects in their research. The book is also valuable for reference libraries and instructors teaching courses in enzyme mechanism.
Novel Uses Of Isotope Effects To Elucidate Enzyme Reaction Mechanisms
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Author : Jeffrey D. Hermes
language : en
Publisher:
Release Date : 1983
Novel Uses Of Isotope Effects To Elucidate Enzyme Reaction Mechanisms written by Jeffrey D. Hermes and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1983 with Enzymes categories.
Nuclear Science Abstracts
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Author :
language : en
Publisher:
Release Date : 1974-07
Nuclear Science Abstracts written by and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1974-07 with Nuclear energy categories.
The Elucidation Of Mechanism And Transition State Structure For Enzyme And Non Enzyme Catalyzed Reactions With The Aid Of Novel Methods For The Measurement Of Oxygen 18 Isotope Effects
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Author : Steven Rosenberg
language : en
Publisher:
Release Date : 1978
The Elucidation Of Mechanism And Transition State Structure For Enzyme And Non Enzyme Catalyzed Reactions With The Aid Of Novel Methods For The Measurement Of Oxygen 18 Isotope Effects written by Steven Rosenberg and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1978 with categories.
Application Of Kinetic Isotope Effects And Theoretical Calculations To The Study Of Interesting Reaction Mechanisms
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Author : Jennifer Sue Hirschi
language : en
Publisher:
Release Date : 2010
Application Of Kinetic Isotope Effects And Theoretical Calculations To The Study Of Interesting Reaction Mechanisms written by Jennifer Sue Hirschi and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2010 with categories.
A variety of biological and organic reaction mechanisms are studied using powerful tools from experimental and theoretical chemistry. These tools include the precise measurement of kinetic isotope effects (KIEs) and the use of theoretical calculations to predict KIEs as well as determine factors that contribute to reaction acceleration and selectivity. Theoretical analysis of the Swain-Schaad relationship involves the prediction of a large number of isotope effects and establishes the semiclassical boundaries of the relationship. Studies on the mechanism of oxidosqualene cyclase involve the determination of a large number of precise KIEs simultaneously. Transition state models for the Sharpless asymmetric epoxidation have been developed that explain the versatility, high selectivities, and ligand accelerated catalysis of the reaction. Theoretical predictions on the proposed enzymatic mechanism of flavin dependent amine oxidation suggest a hydride transfer mechanism and rules out mechanisms involving covalent intermediates. Finally, a theoretical analysis of Diels-Alder reactions successfully describes the unexpected exo selectivity in some of these reactions.