Helps to develop new perspectives and a deeper understanding of organic chemistry Instructors and students alike have praised Perspectives on Structure and Mechanism in Organic Chemistry because it motivates readers to think about organic chemistry in new and exciting ways. Based on the author's first hand classroom experience, the text uses complementary conceptual models to give new perspectives on the structures and reactions of organic compounds. The first five chapters of the text discuss the structure and bonding of stable molecules and reactive intermediates. These are followed by a chapter exploring the methods that organic chemists use to study reaction mechanisms. The remaining chapters examine different types of acid-base, substitution, addition, elimination, pericyclic, and photochemical reactions. This Second Edition has been thoroughly updated and revised to reflect the latest findings in physical organic chemistry. Moreover, this edition features: New references to the latest primary and review literature More study questions to help readers better understand and apply new concepts in organic chemistry Coverage of new topics, including density functional theory, quantum theory of atoms in molecules, Marcus theory, molecular simulations, effect of solvent on organic reactions, asymmetric induction in nucleophilic additions to carbonyl compounds, and dynamic effects on reaction pathways The nearly 400 problems in the text do more than allow students to test their understanding of the concepts presented in each chapter. They also encourage readers to actively review and evaluate the chemical literature and to develop and defend their own ideas. With its emphasis on complementary models and independent problem-solving, this text is ideal for upper-level undergraduate and graduate courses in organic chemistry.

Table of Contents:
Preface xi Acknowledgments xiii Introduction xv Chapter 1 Fundamental Concepts of Organic Chemistry 1 1.1 Atoms and Molecules 1 1.2 Heats of Formation and Reaction 8 1.3 Bonding Models 19 1.4 Complementary Descriptions of the Double Bond 42 1.5 Choosing Models in Organic Chemistry 48 Chapter 2 Stereochemistry 53 2.1 Introduction 53 2.2 Stereoisomerism 56 2.3 Manifestations of Stereoisomerism 86 2.4 Stereotopicity 94 Chapter 3 Conformational Analysis and Molecular Mechanics 113 3.1 Molecular Conformation 113 3.2 Conformational Analysis 119 3.3 Molecular Mechanics 135 3.4 Molecular Strain and Limits to Molecular Stability 155 Chapter 4 Applications of Molecular Orbital Theory and Valence Bond Theory 175 4.1 Introduction to Molecular Orbital Theory 175 4.2 Aromaticity 199 4.3 Contemporary Computational Methods 220 4.4 Valence Bond Theory 237 Chapter 5 Reactive Intermediates 253 5.1 Reaction Coordinate Diagrams 253 5.2 Radicals 256 5.3 Carbenes 278 5.4 Carbocations 289 5.5 Carbanions 310 5.6 Choosing Models of Reactive Intermediates 320 Chapter 6 Methods of Studying Organic Reactions 327 6.1 Molecular Change and Reaction Mechanisms 327 6.2 Methods to Determine Reaction Mechanisms 327 6.3 Applications of Kinetics in Studying Reaction Mechanisms 341 6.4 Arrhenius Theory and Transition-State Theory 348 6.5 Reaction Barriers and Potential Energy Surfaces 360 6.6 Kinetic Isotope Effects 370 6.7 Substituent Effects 385 6.8 Linear Free Energy Relationships 389 Chapter 7 Acid and Base Catalysis of Organic Reactions 413 7.1 Acidity and Basicity of Organic Compounds 413 7.2 Acid and Base Catalysis of Chemical Reactions 433 7.3 Acid and Base Catalysis of Reactions of Carbonyl Compounds and Carboxylic Acid Derivatives 439 Chapter 8 Substitution Reactions 469 8.1 Introduction 469 8.2 Nucleophilic Aliphatic Substitution 472 8.3 Electrophilic Aromatic Substitution 518 8.4 Nucleophilic Aromatic and Vinylic Substitution 527 Chapter 9 Addition Reactions 551 9.1 Introduction 551 9.2 Addition of Halogens to Alkenes 553 9.3 Other Addition Reactions 585 Chapter 10 Elimination Reactions 633 10.1 Introduction 633 10.2 Dehydrohalogenation and Related 1,2-Elimination Reactions 638 10.3 Other 1,2-Elimination Reactions 665 Chapter 11 Pericyclic Reactions 697 11.1 Introduction 697 11.2 Electrocyclic Transformations 702 11.3 Sigmatropic Reactions 715 11.4 Cycloaddition Reactions 731 11.5 Other Concerted Reactions 747 11.6 A General Selection Rule for Pericyclic Reactions 753 11.7 Alternative Conceptual Models for Concerted Reactions 756 Chapter 12 Photochemistry 787 12.1 Photophysical Processes 787 12.2 Fundamentals of Photochemical Kinetics 804 12.3 Physical Properties of Excited States 810 12.4 Representative Photochemical Reactions 818 12.5 Some Applications of Organic Photochemistry 853 Problems 862 References for Selected Problems 871 Permissions 883 Author Index 895 Subject Index 927