Modern Physical Organic Chemistry / Edition 1

by Eric V. Anslyn

Overview

Anslyn (chemistry, U. of Texas, Austin) and Dougherty (chemistry, California Institute of Technology) have written a textbook that will provide students with a thorough knowledge of current research and issues, as well as a grounding in the fundamentals of the field. The chapters contain a number of inset boxes that note the chapter topic's connection to relevant fields, its use in research, and other related information. Each chapter concludes with 25 or more exercises and a bibliography. There are 17 chapters in all, with topics that include stereochemistry, energy surfaces and kinetic analyses, advanced concepts in electronic structure theory, and photochemistry. This is a substantial, well thought-out text, suitable for a one-year course. Annotation ©2005 Book News, Inc., Portland, OR

Product Details

ISBN-13:	2901891389312
Publisher:	University Science Books
Publication date:	08/15/2005
Edition description:	2006
Pages:	1104
Product dimensions:	8.88(w) x 11.12(h) x 2.17(d)

About the Author

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.

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.

Table of Contents

Chapter 1: Introduction to Structure and Models of BondingIntent and Purpose.1.1 A Review of Basic Bonding Concepts.1.2 A More Modern Theory of Organic Bonding1.3 Orbital Mixing – Building Larger Molecules1.4 Bonding and Structure of Reactive Intermediates1.5 A Very Quick Look at Organometallic and Inorganic BondingChapter 2: Strain and StabilityIntent and Purpose2.1 Thermochemistry of Stable Molecules2.2 Thermochemistry of Reactive Intermediates2.3 Relationships between Structure and Energetics; Basic Conformational Analysis2.4 Electronic Effects2.5 Highly Strained Molecules2.6 Molecular MechanicsChapter 3: Solutions and Noncovalent Binding ForcesIntent and Purpose3.1 Solvent and Solution Properties3.2 Binding Forces3.3 Computational Modeling of SolvationChapter 4: Molecular Recognition and Supramolecular ChemistryIntent and Purpose4.1 Thermodynamic Analyses of Binding Phenomena4.2 Molecular Recognition4.3 Supramolecular ChemistryChapter 5: Acid-Base ChemistryIntent and Purpose5.1 Brønsted Acid and Base Chemistry5.2 Aqueous Solutions5.3 Nonaqueous Systems5.4 Predicting Acid Strength5.5 Acids-Bases of Bioorganic Interest5.6 Lewis Acids/Bases and Electrophiles/NucleophilesChapter 6: StereochemistryIntent and Purpose6.1 Stereogenicity and Stereoisomerism6.2 Symmetry and Stereochemistry6.3 Topicity Relationships6.4 Reaction Stereochemistry: Stereoselectivity and Stereospecificity6.5 Symmetry and Timescale6.6 Topological and Supramolecular Stereochemistry6.7 Stereochemical Issues in Polymer Chemistry6.8 Stereochemical Issues in Chemical BiologySummary and OutlookChapter 7: Energy Surfaces and Kinetic AnalysesIntent and Purpose:7.1 Energy Surfaces and Related Concepts7.2 Transition State Theory (TST), and Related Topics7.3 Postulates and Principles Related to Kinetic Analysis7.4 Kinetic Experiments7.5 Complex Reactions – Deciphering Mechanisms7.6 Methods for Following Kinetics7.7 Calculating Rate Constants7.8 Considering Multiple Reaction CoordinatesSummary and OutlookChapter 8: Experiments Related to Thermodynamics and KineticsIntent and Purpose8.1 Isotope Effects8.2 Substituent Effects8.3 Hammett Plots, The Most Common LFER. A General Method for Examining Changes in Charges During a Reaction8.4 Other Linear Free Energy Relationships8.5 Acid/Base Related Effects / Brønsted Relationships8.6 Why do Linear Free Energy Relationships Work? 8.7 Summary of Linear Free Energy Relationships8.8 Miscellaneous Experiments for Studying MechanismsChapter 9: CatalysisIntent and Purpose9.1 General Principles of Catalysis9.2 Forms of Catalysis9.3 Brønsted Acid/Base Catalysis9.4 Enzymatic CatalysisChapter 10: Organic Reaction Mechanisms Part 1: Reactions Involving Additions and/or EliminationsIntent and Purpose10.1 Predicting Organic Reactivity10.2 Hydration of Carbonyl Structures10.3 Electrophilic Addition of Water to Alkenes and Alkynes: Hydration10.4 Electrophilic Addition of Hydrogen Halides to Alkenes and Alkynes10.5 Electrophilic Addition of Halogens to Alkenes10.6 Hydroboration10.7 Epoxidation10.8 Nucleophilic Additions to Carbonyl Compounds10.9 Nucleophilic Additions to Olefins10.10 Radical Additions to Unsaturated Systems10.11 Carbene Additions and Insertions10.12 Eliminations to Form Carbonyls or “Carbonyl-Like” Intermediates10.13 Elimination Reactions for Aliphatic Systems, Formation of Alkenes10.14 Eliminations from Radical Intermediates10.15 Addition of Nitrogen Nucleophiles To Carbonyl Structures, Followed by Elimination10.16 Addition of Carbon Nucleophiles, Followed by Elimination – The Wittig Reaction10.17 Acyl Transfers10.18 Electrophilic Aromatic Substitution10.19 Nucleophilic Aromatic Substitution10.20 Reactions Involving Benzyne10.21 The SRN1 Reaction on Aromatic Rings10.22 Radical Aromatic SubstitutionsChapter 11: Organic Reaction Mechanisms Part II: Substitutions at Aliphatic Centers and Thermal Isomerizations/RearrangementsIntent and Purpose11.1 Tautomerization11.2 a-Halogenation11.3 a-Alkylations11.4 The Aldol Reaction11.5 Nucleophilic Aliphatic Substitution Reactions11.6 Substitution – Radical – Nucleophilic11.7 Radical Aliphatic Substitutions11.8 Migrations to Electrophilic Carbon11.9 Migrations to Electrophilic Heteroatoms11.10 The Favorskii Rearrangement and Other Carbanion Rearrangements11.11 Rearrangements Involving Radicals11.12 Rearrangements and Isomerizations Involving BiradicalsChapter 12: Organotransition Metal Reaction Mechanisms and CatalysisIntent and Purpose:12.1 The Basics of Organometallic Complexes12.2 Common Organometallic Reactions12.3 Combining the Individual Reactions into Overall Transformations and CyclesChapter 13. Organic Polymer and Materials ChemistryIntent and Purpose13.1 Structural Issues in Materials Chemistry13.2 Common Polymerization MechanismsChapter 14. Advanced Concepts in Electronic Structure TheoryIntent and Purpose14.1 Introductory Quantum Mechanics14.2 Calculational Methods – Solving the Schrödinger Equation for Complex Systems14.3 A Brief Overview of the Implementation and Results of HMOT14.4 Perturbation Theory – Orbital Mixing Rules14.5 Some Topics in Organic Chemistry for Which Molecular Orbital Theory Lends Important Insights14.6 Organometallic ComplexesChapter 15: Thermal Pericyclic ReactionsIntent and Purpose15.1 Background15.2 A Detailed Analysis of Two Simple Cycloadditions15.3. Cycloadditions15.4 Electrocyclic Reactions15.5 Sigmatropic Rearrangements15.6 Chelotropic Reactions15.7 In Summary, Applying the RulesSummary and OutlookChapter 16: PhotochemistryIntent and Purpose16.1 Photophysical Processes – the Jablonski Diagram16.2 Bimolecular Photophysical Processes16.3 Photochemical Reactions16.4 Chemiluminescence16.5 Singlet OxygenChapter 17: Electronic Organic MaterialsIntent and Purpose17.1 Theory17.2 Conducting Polymers17.3 Organic Magnetic Materials17.4 Superconductivity17.5 Nonlinear Optics (NLO)17.6 Photoresists17.7 Summary

Editorial Reviews

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

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

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

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

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

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

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

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

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