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Modern Physical Organic Chemistry

Eric V. Anslyn University of Texas, Austin
Dennis A. Dougherty California Institute of Technology

This is the first modern textbook, written in the 21st century, to make explicit the many connections between physical organic chemistry and critical fields such as organometallic chemistry, materials chemistry, bioorganic chemistry, and biochemistry.

ISBN 978-1-891389-31-3
eISBN 978-1-891389-48-1
Copyright 2006
1104 pages, Hard Cover


This is the first modern textbook, written in the 21st century, to make explicit the many connections between physical organic chemistry and critical fields such as organometallic chemistry, materials chemistry, bioorganic chemistry, and biochemistry. In the latter part of the 20th century, the field of physical organic chemistry went through dramatic changes, with an increased emphasis on noncovalent interactions and their roles in molecular recognition, supramolecular chemistry, and biology; the development of new materials with novel structural features; and the use of computational methods. Contemporary chemists must be just as familiar with these newer fields as with the more established classical topics.

This completely new landmark text is intended to bridge that gap. In addition to covering thoroughly the core areas of physical organic chemistry – structure and mechanism – the book will escort the practitioner of organic chemistry into a field that has been thoroughly updated. The foundations and applicabilities of modern computational methods are also developed.

Written by two distinguished researchers in this field, Modern Physical Organic Chemistry can serve as a text for a year-long course targeted to advanced undergraduates or first-year graduate students, as well as for a variety of shorter courses on selected aspects of the field. It will also serve as a landmark new reference text, and as an introduction to many of the more advanced topics of interest to modern researchers.

Translated into Chinese

Link to Solutions Manual

Table of Contents

Chapter 1: Introduction to Structure and Models of Bonding
Intent and Purpose.
1.1 A Review of Basic Bonding Concepts.
1.2 A More Modern Theory of Organic Bonding
1.3 Orbital Mixing – Building Larger Molecules
1.4 Bonding and Structure of Reactive Intermediates
1.5 A Very Quick Look at Organometallic and Inorganic Bonding

Chapter 2: Strain and Stability
Intent and Purpose
2.1 Thermochemistry of Stable Molecules
2.2 Thermochemistry of Reactive Intermediates
2.3 Relationships between Structure and Energetics; Basic Conformational Analysis
2.4 Electronic Effects
2.5 Highly Strained Molecules
2.6 Molecular Mechanics

Chapter 3: Solutions and Noncovalent Binding Forces
Intent and Purpose
3.1 Solvent and Solution Properties
3.2 Binding Forces
3.3 Computational Modeling of Solvation

Chapter 4: Molecular Recognition and Supramolecular Chemistry
Intent and Purpose
4.1 Thermodynamic Analyses of Binding Phenomena
4.2 Molecular Recognition
4.3 Supramolecular Chemistry

Chapter 5: Acid-Base Chemistry
Intent and Purpose
5.1 Brønsted Acid and Base Chemistry
5.2 Aqueous Solutions
5.3 Nonaqueous Systems
5.4 Predicting Acid Strength
5.5 Acids-Bases of Bioorganic Interest
5.6 Lewis Acids/Bases and Electrophiles/Nucleophiles

Chapter 6: Stereochemistry
Intent and Purpose
6.1 Stereogenicity and Stereoisomerism
6.2 Symmetry and Stereochemistry
6.3  Topicity Relationships
6.4  Reaction Stereochemistry:  Stereoselectivity and Stereospecificity
6.5  Symmetry and Timescale
6.6  Topological and Supramolecular Stereochemistry
6.7 Stereochemical Issues in Polymer Chemistry
6.8 Stereochemical Issues in Chemical Biology
Summary and Outlook

Chapter 7: Energy Surfaces and Kinetic Analyses
Intent and Purpose:
7.1 Energy Surfaces and Related Concepts
7.2 Transition State Theory (TST), and Related Topics
7.3 Postulates and Principles Related to Kinetic Analysis
7.4 Kinetic Experiments
7.5 Complex Reactions – Deciphering Mechanisms
7.6 Methods for Following Kinetics
7.7 Calculating Rate Constants
7.8 Considering Multiple Reaction Coordinates
Summary and Outlook

Chapter 8: Experiments Related to Thermodynamics and Kinetics
Intent and Purpose
8.1 Isotope Effects
8.2 Substituent Effects
8.3 Hammett Plots, The Most Common LFER. A General Method for Examining Changes in Charges During a Reaction
8.4 Other Linear Free Energy Relationships
8.5 Acid/Base Related Effects / Brønsted Relationships
8.6 Why do Linear Free Energy Relationships Work?
8.7 Summary of Linear Free Energy Relationships
8.8 Miscellaneous Experiments for Studying Mechanisms

Chapter 9: Catalysis
Intent and Purpose
9.1 General Principles of Catalysis
9.2 Forms of Catalysis
9.3 Brønsted Acid/Base Catalysis
9.4 Enzymatic Catalysis

Chapter 10: Organic Reaction Mechanisms Part 1: Reactions Involving Additions and/or Eliminations
Intent and Purpose
10.1 Predicting Organic Reactivity
10.2 Hydration of Carbonyl Structures
10.3 Electrophilic Addition of Water to Alkenes and Alkynes: Hydration
10.4 Electrophilic Addition of Hydrogen Halides to Alkenes and Alkynes
10.5 Electrophilic Addition of Halogens to Alkenes
10.6 Hydroboration
10.7 Epoxidation
10.8 Nucleophilic Additions to Carbonyl Compounds
10.9 Nucleophilic Additions to Olefins
10.10 Radical Additions to Unsaturated Systems
10.11 Carbene Additions and Insertions
10.12 Eliminations to Form Carbonyls or “Carbonyl-Like” Intermediates
10.13 Elimination Reactions for Aliphatic Systems, Formation of Alkenes
10.14 Eliminations from Radical Intermediates
10.15 Addition of Nitrogen Nucleophiles To Carbonyl Structures, Followed by Elimination
10.16 Addition of Carbon Nucleophiles, Followed by Elimination – The Wittig Reaction
10.17 Acyl Transfers
10.18 Electrophilic Aromatic Substitution
10.19 Nucleophilic Aromatic Substitution
10.20 Reactions Involving Benzyne
10.21 The SRN1 Reaction on Aromatic Rings
10.22 Radical Aromatic Substitutions

Chapter 11: Organic Reaction Mechanisms Part II: Substitutions at Aliphatic Centers and Thermal Isomerizations/Rearrangements
Intent and Purpose
11.1 Tautomerization
11.2 a-Halogenation
11.3 a-Alkylations
11.4 The Aldol Reaction
11.5 Nucleophilic Aliphatic Substitution Reactions
11.6 Substitution – Radical – Nucleophilic
11.7 Radical Aliphatic Substitutions
11.8 Migrations to Electrophilic Carbon
11.9 Migrations to Electrophilic Heteroatoms
11.10 The Favorskii Rearrangement and Other Carbanion Rearrangements
11.11 Rearrangements Involving Radicals
11.12 Rearrangements and Isomerizations Involving Biradicals

Chapter 12: Organotransition Metal Reaction Mechanisms and Catalysis
Intent and Purpose:
12.1 The Basics of Organometallic Complexes
12.2 Common Organometallic Reactions
12.3 Combining the Individual Reactions into Overall Transformations and Cycles

Chapter 13. Organic Polymer and Materials Chemistry
Intent and Purpose
13.1 Structural Issues in Materials Chemistry
13.2 Common Polymerization Mechanisms

Chapter 14.  Advanced Concepts in Electronic Structure Theory
Intent and Purpose
14.1 Introductory Quantum Mechanics
14.2 Calculational Methods – Solving the Schrödinger Equation for Complex Systems
14.3  A Brief Overview of the Implementation and Results of HMOT
14.4  Perturbation Theory – Orbital Mixing Rules
14.5 Some Topics in Organic Chemistry for Which Molecular Orbital Theory Lends Important Insights
14.6 Organometallic Complexes

Chapter 15: Thermal Pericyclic Reactions
Intent and Purpose
15.1 Background
15.2 A Detailed Analysis of Two Simple Cycloadditions
15.3. Cycloadditions
15.4 Electrocyclic Reactions
15.5  Sigmatropic Rearrangements
15.6 Chelotropic Reactions
15.7 In Summary, Applying the Rules
Summary and Outlook

Chapter 16: Photochemistry
Intent and Purpose
16.1 Photophysical Processes – the Jablonski Diagram
16.2 Bimolecular Photophysical Processes
16.3 Photochemical Reactions
16.4 Chemiluminescence
16.5 Singlet Oxygen

Chapter 17:  Electronic Organic Materials
Intent and Purpose
17.1  Theory
17.2 Conducting Polymers
17.3 Organic Magnetic Materials
17.4 Superconductivity
17.5 Nonlinear Optics (NLO)
17.6 Photoresists
17.7 Summary

View All Frontmatter in PDF Format
Preview Chapter 6 on Stereochemistry in PDF Format
PDF file for pg. 515


“Students and others are emphatically recommended to read this excellent book. “Anslyn & Dougherty” should be in every chemical library. It will be a valuable aid to every student, but it can also be strongly recommended for all research chemists as a reference source on physical-organic chemistry. The book is a worthwhile investment.”
-Angewandte Chemie, 2006, 45, 1019-1020

“MPOC is the most well rounded textbook on physical organic chemistry that I have seen. The authors are to be commended for their six year “labor of love.”
-J. Chem. Ed, 2006, March, Vol. 83, No. 3, pg. 387

“Modern Physical Organic Chemistry is a most impressive resource for researchers and teachers, and yet it also offers an accessible entree into the topics for advanced undergraduates and postgraduates. Each chapter ends with a “Summary and Outlook”, an excellent array of problems and exercises and a comprehensive bibliography that often refers to the review literature. This type of text is often not easily accessible to the undergraduate reader, but I found this one to be well structured and very pleasant to read. Modern Physical Organic Chemistry is a book I am very happy to have on my shelf.”
-The Times Higher, 2006

“Spectacular! Congratulations! I plan to recommend it to all of my research group members and to those students in my class who are getting hooked on organic chemistry. This is going to be a winner.”
-Peter Vollhardt, University of California at Berkeley

“Anslyn and Dougherty have done an admirable and scholarly job to put the essence of this important subject between the covers of a single text. I can enthusiastically recommend the text for anyone who is teaching a course dealing with the essentials of physical organic chemistry and more.”
-Nicholas J. Turro, Columbia University

“The text will certainly inspire those coming to physical organic chemistry as a first love, as well as those coming from a bordering discipline who wish to acquire the insight that physical organic chemistry can provide.”
-Barry Carpenter, Cornell University

“This much needed text places physical organic chemistry in its most modern context as the foundation of not only organic chemistry, but as the basis for understanding the most current research in supramolecular chemistry, organic materials science, catalysis, and organometallics. This book is the new authoritative physical organic resource that will benefit researchers, students, and teachers alike.”
-Timothy M. Swager, Massachusetts Institute of Technology

“By building the text from the ground up, the authors have managed to incorporate modern applications of the theories of physical organic chemistry throughout, in a way that no revision of an existing text can hope to accomplish.”
-Thomas Poon, Claremont Colleges

“This is a high quality book that fills a real need in our field, and that makes every other book in this area immediately obsolete. Congratulations to the authors on a remarkable achievement!”
-David I. Schuster, New York University

Eric V. Anslyn University of Texas, Austin

Eric V. Anslyn received his PhD in Chemistry from the California Institute of Technology under the direction of Robert Grubbs. After completing post-doctoral work with Ronald Breslow at Columbia University, he joined the faculty at the University of Texas at Austin, where he became a Full Professor in 1999. He currently holds four patents and is the recipient of numerous awards and honors, including the Presidential Young Investigator, the Alfred P. Sloan Research Fellow, the Searle Scholar, the Dreyfus Teacher-Scholar Award, and the Jean Holloway Award for Excellence in Teaching. He is also the Associate Editor for the Journal of the American Chemical Society and serves on the editorial boards of Supramolecular Chemistry and the Journal of Supramolecular Chemistry. His primary research is in physical organic chemistry and bioorganic chemistry, with specific interests in catalysts for phosphoryl and glycosyl transfers, receptors for carbohydrates and enolates, single and multi-analyte sensors – the development of an electronic tongue, and synthesis of polymeric molecules that exhibit unique abiotic secondary structure.

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Dennis A. Dougherty California Institute of Technology

Dennis A. Dougherty received a PhD from Princeton with Kurt Mislow, followed by a year of postdoctoral study with Jerome Berson at Yale. In 1979 he joined the faculty at the California Institute of Technology, where he is now George Grant Hoag Professor of Chemistry. Dougherty's extensive research interests have taken him to many fronts, but he is perhaps best known for development of the cation-π interaction, a novel but potent noncovalent binding interaction. More recently, he has addressed molecular neurobiology, developing the in vivo nonsense suppression method for unnatural amino acid incorporation into proteins expressed in living cells. This powerful new tool enables “physical organic chemistry on the brain” - chemical-scale studies of the molecules of memory, thought, and sensory perception and the targets of treatments for Alzheimer's disease, Parkinson's disease, schizophrenia, learning and attention deficits, and drug addiction. His group is now working on extensive experimental and computational studies of the bacterial mechanosensitive channels MscL and MscS, building off the crystal structures of these channels recently reported by the Rees group at Caltech.

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