Organic Mechanisms - Reactions, Methodology, and Biological Applications

Informationen zum Autor XIAOPING SUN, PhD, is Professor of Chemistry at the University of Charleston. Dr. Sun has more than ten years of experience teaching advanced organic chemistry and biochemistry. His research focuses on studying the mechanisms of chemical reactions. Dr. Sun is the recipient of a research grant from the National Science Foundation. Klappentext Instills a deeper understanding of how and why organic reactions happenIntegrating reaction mechanisms, synthetic methodology, and biological applications, Organic Mechanisms gives organic chemists the tools needed to perform seamless organic reactions. By explaining the underlying mechanisms of organic reactions, author Xiaoping Sun makes it possible for readers to gain a deeper understanding of not only chemical phenomena, but also the ability to develop new synthetic methods. Moreover, by emphasizing biological applications, this book enables readers to master both advanced organic chemistry theory and practice.Organic Mechanisms consists of ten chapters, beginning with a review of fundamental physicochemical principles that are essential for understanding the nature of organic mechanisms. Each one of the remaining chapters is devoted to a major class of organic reactions, including:* Aliphatic C-H bond functionalization* Functionalization of the alkene C=C bond by cycloaddition reactions* Nucleophilic substitutions on sp3-hybridized carbons* Nucleophilic additions and substitutions on carbonyl groups* Reactivity of the alpha-hydrogen to carbonyl groups* RearrangementsA brief review of basic organic chemistry begins each chapter, helping readers move from fundamental concepts to an advanced understanding of reaction mechanisms. Key mechanisms are illustrated by expertly drawn figures highlighting microscopic details. End-of-chapter problems enable readers to put their newfound knowledge into practice by solving key problems in organic reactions with the use of mechanistic studies, and a Solutions Manual is available online for course instructors.Thoroughly referenced and current with recent findings in organic reaction mechanisms, Organic Mechanisms is recommended for upper-level undergraduates and graduate students in advanced organic chemistry, as well as for practicing chemists who want to further explore the mechanistic aspects of organic reactions.Emphasizing mechanistic aspects of organic reactions, Organic Mechanisms provides a useful guide for how to analyze, understand, approach, and solve the problems of organic reactions with the help of mechanistic studies. Inhaltsverzeichnis Preface xiii1 Fundamental Principles 11.1 Reaction Mechanisms and their Importance 11.2 Elementary (Concerted) and Stepwise Reactions 21.3 Molecularity 41.4 Kinetics 51.5 Thermodynamics 131.6 The Transition State 171.7 The Molecular Orbital Theory 191.8 Electrophiles/Nucleophiles versus Acids/Bases 291.9 Isotope Labeling 35Problems 38References 402 The Aliphatic C H Bond Functionalization 412.1 Alkyl Radicals: Bonding and their Relative Stability 422.2 Radical Halogenations of the C H Bonds on sp3-Hybridized Carbons: Mechanism and Nature of the Transition States 472.3 Energetics of the Radical Halogenations of Alkanes and their Regioselectivity 512.4 Kinetics of Radical Halogenations of Alkanes 562.5 Radical Initiators 612.6 Transition-Metal-Compounds-Catalyzed Alkane C H Bond Activation and Functionalization 642.7 Superacids-Catalyzed Alkane C H Bond Activation and Functionalization 682.8 Nitration of Aliphatic C H Bonds via the Nitronium NO2 + Ion 692.9 Enzyme-Catalyzed Alkane C H Bond Activation and Functionalization: Biochemical Methods 71Problems 75References 773 Functionalization of the Alkene C C Bond by Electrophilic Additions 783.1 Markovnikov Additions via Intermediate Carbocations 793.2 Electrophilic Addition of Hydrogen Halides to Conjugated Dienes 953.3 Non-Markovni...

List of contents

Preface xiii1 Fundamental Principles 11.1 Reaction Mechanisms and their Importance 11.2 Elementary (Concerted) and Stepwise Reactions 21.3 Molecularity 41.4 Kinetics 51.5 Thermodynamics 131.6 The Transition State 171.7 The Molecular Orbital Theory 191.8 Electrophiles/Nucleophiles versus Acids/Bases 291.9 Isotope Labeling 35Problems 38References 402 The Aliphatic C H Bond Functionalization 412.1 Alkyl Radicals: Bonding and their Relative Stability 422.2 Radical Halogenations of the C H Bonds on sp3-Hybridized Carbons: Mechanism and Nature of the Transition States 472.3 Energetics of the Radical Halogenations of Alkanes and their Regioselectivity 512.4 Kinetics of Radical Halogenations of Alkanes 562.5 Radical Initiators 612.6 Transition-Metal-Compounds-Catalyzed Alkane C H Bond Activation and Functionalization 642.7 Superacids-Catalyzed Alkane C H Bond Activation and Functionalization 682.8 Nitration of Aliphatic C H Bonds via the Nitronium NO2 + Ion 692.9 Enzyme-Catalyzed Alkane C H Bond Activation and Functionalization: Biochemical Methods 71Problems 75References 773 Functionalization of the Alkene C C Bond by Electrophilic Additions 783.1 Markovnikov Additions via Intermediate Carbocations 793.2 Electrophilic Addition of Hydrogen Halides to Conjugated Dienes 953.3 Non-Markovnikov Radical Addition 963.4 Hydroboration: Concerted, Non-Markovnikov syn-Addition 973.5 Transition-Metal-Catalyzed Hydrogenation of the Alkene C C Bond (syn-Addition) 1073.6 Halogenation of the Alkene C C Bond (Anti-Addition): Mechanism and Its Stereochemistry 113Problems 117References 1204 Functionalization of the Alkene C C Bond by Cycloaddition Reactions 1214.1 Cycloadditions of the Alkene C C Bond to Form Three-Membered Rings 1224.2 Cycloadditions to Form Four-Membered Rings 1284.3 Diels-Alder Cycloadditions of the Alkene C C Bond to Form Six-Membered Rings 1314.4 1,3-Dipolar Cycloadditions of the C C and other Multiple Bonds to Form Five-Membered Rings 1424.5 Pericyclic Reactions 154Problems 158References 1615 The Aromatic C H Bond Functionalization and Related Reactions 1625.1 Aromatic Nitration: All Reaction Intermediates and Full Mechanism for the Aromatic C H Bond Substitution by Nitronium (NO2 +) and Related Electrophiles 1635.2 Mechanisms and Synthetic Utility for Aromatic C H Bond Substitutions by Other Related Electrophiles 1675.3 The Electrophilic Aromatic C H Bond Substitution Reactions via SN1 and SN2 Mechanisms 1745.4 Substituent Effects on the Electrophilic Aromatic Substitution Reactions 1815.5 Isomerizations Effected by the Electrophilic Aromatic Substitution Reactions 1875.6 Electrophilic Substitution Reactions on the Aromatic Carbon-Metal Bonds: Mechanisms and Synthetic Applications 1915.7 Nucleophilic Aromatic Substitution via a Benzyne (aryne) Intermediate: Functional Group Transformations on Aromatic Rings 1935.8 Nucleophilic Aromatic Substitution via an Anionic Meisenheimer Complex 1975.9 Biological Applications of Functionalized Aromatic Compounds 200Problems 204References 2076 Nucleophilic Substitutions on sp3-Hybridized Carbons: Functional Group Transformations 2096.1 Nucleophilic Substitution on Mono-Functionalized sp3-Hybridized Carbon 2096.2 Functional Groups which are Good and Poor Leaving Groups 2116.3 Good and Poor Nucleophiles 2136.4 SN2 Reactions: Kinetics, Mechanism, and Stereochemistry 2156.5 Analysis of the SN2 Mechanism Using Symmetry Rules and Molecular Orbital Theory 2256.6 SN1 Reactions: Kinetics, Mechanism, and Product Development 2296.7 Competition between SN1 and SN2 Reactions 2376.8 Some Useful SN1 and SN2 Reactions: Mechanisms and Synthetic Perspectives 2416.9 Biological Applications of Nucleophilic Substitution Reactions 251Problems 256References 2597 Eliminations 2607.1 E2 Elimination: Bimolecular -Elimination of H/LG and Its Regiochemistry and Stereochemistry 2617.2 Analysis of the E2 Mechanism Using Symmetry Rules and Molecular Orbital Theory 2687.3 Basicity versus Nucleophilicity for Various Anions 2717.4 Competition of E2 and SN2 Reactions 2747.5 E1 Elimination: Stepwise -Elimination of H/LG via an Intermediate Carbocation and Its Rate Law 2767.6 Special -Elimination Reactions 2837.7 Elimination of LG1/LG2 in the Compounds that Contain Two Functional Groups 2867.8 -Elimination Giving a Carbene: A Mechanistic Analysis Using Symmetry Rules and Molecular Orbital Theory 2887.9 E1cb Elimination and its Biological Applications 288Problems 294References 2978 Nucleophilic Additions and Substitutions on Carbonyl Groups 2988.1 Nucleophilic Additions and Substitutions of Carbonyl Compounds 2988.2 Nucleophilic Additions of Aldehydes and Ketones and their Biological Applications 3018.3 Biological Hydride Donors NAD(P)H and FADH2 3168.4 Activation of Carboxylic Acids via Nucleophilic Substitutions on the Carbonyl Carbons 3208.5 Nucleophilic Substitutions of Acyl Derivatives and their Biological Applications 3278.6 Reduction of Acyl Derivatives by Hydride Donors 3358.7 Kinetics of the Nucleophilic Addition and Substitution of Acyl Derivatives 337Problems 340References 3429 Reactivity of the -Hydrogen to Carbonyl Groups 3449.1 Formation of Enolates and their Nucleophilicity 3449.2 Alkylation of Carbonyl Compounds (Aldehydes, Ketones, and Esters) via Enolates and Hydrazones 3499.3 Aldol Reactions 3549.4 Acylation Reactions of Esters via Enolates: Mechanism and Synthetic Utility 3679.5 Roles of Enolates in Metabolic Processes in Living Organisms 373Problems 376References 37810 Rearrangements 38010.1 Major Types of Rearrangements 38010.2 Rearrangement of Carbocations: 1,2-Shift 38110.3 Neighboring Leaving Group-Facilitated 1,2-Rearrangement 39010.4 Carbene Rearrangement: 1,2-Rearrangement of Hydrogen Facilitated by a Lone Pair of Electrons 39910.5 Claisen Rearrangement 40110.6 Photochemical Isomerization of Alkenes and its Biological Applications 40310.7 Rearrangement of Carbon-Nitrogen-Sulfur-Containing Heterocycles 405Problems 409References 411Index 413

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"Summing Up: Recommended. Highly recommended. Upper-division undergraduates and above." ( Choice , 1 May 2014)

Product details

• Authors: Xiaoping Sun
• Publisher: Wiley, John and Sons Ltd
• Languages: English
• Product format: Hardback
• Released: 28.06.2013
• EAN: 9781118065648
• ISBN: 978-1-118-06564-8
• No. of pages: 432
• Subject: Natural sciences, medicine, IT, technology > Chemistry > Organic chemistry