Modern Physical Organic Chemistry
by Anslyn, Dougherty
ISBN: 9781891389313 | Copyright 2005
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his 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 _x0013_ structure and mechanism _x0013_ 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
Published under the University Science Books imprint
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Front Cover (pg. i) | |
Front & Back Endsheets (pg. ii) | |
Abbreviated Contents (pg. ix) | |
Table of Contents (pg. x) | |
List of Highlights (pg. xxii) | |
Preface (pg. xxvi) | |
Acknowledgments (pg. xxviii) | |
A Note to the Instructor (pg. xxix) | |
Part I: Molecular Structure and Thermodynamics (pg. 1) | |
1. Introduction to Structure and Models of Bonding (pg. 2) | |
1.1 A Review of Basic Bonding Concepts (pg. 3) | |
1.2 A More Modern Theory of Organic Bonding (pg. 25) | |
1.3 Orbital Mixing -- Building Larger Molecules (pg. 34) | |
1.4 Bonding and Structures of Reactive Intermediates (pg. 51) | |
1.5 A Very Quick Look at Organometallic and Inorganic Bonding (pg. 58) | |
Summary & Outlook (pg. 60) | |
Exercises (pg. 61) | |
Further Reading (pg. 63) | |
2. Strain and Stability (pg. 64) | |
2.1 Thermochemistry of Stable Molecules (pg. 64) | |
2.2 Thermochemistry of Reactive Intermediates (pg. 81) | |
2.3 Relationships Between Structure and Energetics - Basic Conformational Analysis (pg. 91) | |
2.4 Electronic Effects (pg. 111) | |
2.5 Highly-Strained Molecules (pg. 123) | |
2.6 Molecular Mechanics (pg. 127) | |
Summary & Outlook (pg. 136) | |
Exercises (pg. 137) | |
Further Reading (pg. 142) | |
3. Solutions and Non-Covalent Binding Forces (pg. 144) | |
3.1 Solvent and Solution Properties (pg. 144) | |
3.2 Binding Forces (pg. 161) | |
3.3 Computational Modeling of Solvation (pg. 193) | |
Summary & Outlook (pg. 200) | |
Exercises (pg. 201) | |
Further Reading (pg. 203) | |
4. Molecular Recognition and Supramolecular Chemistry (pg. 206) | |
4.1 Thermodynamic Analyses of Binding Phenomena (pg. 206) | |
4.2 Molecular Recognition (pg. 221) | |
4.3 Supramolecular Chemistry (pg. 242) | |
Summary & Outlook (pg. 251) | |
Exercises (pg. 252) | |
Further Reading (pg. 255) | |
5. Acid–Base Chemistry (pg. 258) | |
5.1 Bronsted Acid-Base Chemistry (pg. 258) | |
5.2 Aqueous Solutions (pg. 260) | |
5.3 Nonaqueous Systems (pg. 270) | |
5.4 Predicting Acid Strength in Solution (pg. 275) | |
5.5 Acids and Bases of Biological Interest (pg. 284) | |
5.6 Lewis Acids/Bases and Electrophioles/Nucleophiles (pg. 287) | |
Summary & Outlook (pg. 291) | |
Exercises (pg. 291) | |
Further Reading (pg. 293) | |
6. Stereochemistry (pg. 296) | |
6.1 Stereogenicity and Stereoisomerism (pg. 296) | |
6.2 Symmetry and Stereochemistry (pg. 310) | |
6.3 Topicity Relationships (pg. 314) | |
6.4 Reaction Stereochemistry: Stereoselectivity and Stereospecificity (pg. 316) | |
6.5 Symmetry and Time Scale (pg. 321) | |
6.6 Topological and Supramolecular Stereochemistry (pg. 322) | |
6.7 Stereochemical Issues in Polymer Chemistry (pg. 330) | |
6.8 Stereochemical Issues in Chemical Biology (pg. 332) | |
6.9 Stereochemical Terminology (pg. 339) | |
Summary & Outlook (pg. 343) | |
Exercises (pg. 343) | |
Further Reading (pg. 349) | |
Part II: Reactivity, Kinetics and Mechanisms (pg. 352) | |
7. Energy Surfaces and Kinetic Analyses (pg. 354) | |
7.1 Energy Surfaces and Related Concepts (pg. 355) | |
7.2 Transtion State Theory (TST) and Related Topics (pg. 364) | |
7.3 Postulates and Principles Related to Kinetic Analysis (pg. 373) | |
7.4 Kinetic Experiments (pg. 381) | |
7.5 Complex Reactions -- Deciperhing Mechanisms (pg. 389) | |
7.6 Methods for Following Kinetics (pg. 396) | |
7.7 Calculating Rate Constants (pg. 402) | |
7.8 Considering Multiple Reaction Coordinates (pg. 406) | |
Summary & Outlook (pg. 412) | |
Exercises (pg. 412) | |
Further Reading (pg. 416) | |
8. Experiments Related to Thermodynamics and Kinetics (pg. 420) | |
8.1 Isotope Effects (pg. 420) | |
8.2 Substituent Effects (pg. 440) | |
8.3 Hammett Plots -- The Most Common LFER. A General Method for Examining Changes in Charges During a Reaction (pg. 444) | |
8.4 Other Linear Free Energy Relationships (pg. 453) | |
8.5 Acid-Base Related Effects -- Bronsted Relationships (pg. 463) | |
8.6 Why do Linear Free Energy Relationships Work? (pg. 465) | |
8.7 Summary of Linear Free Energy Relationships (pg. 469) | |
8.8 Miscellaneous Experiments for Studying Mechanisms (pg. 470) | |
Summary & Outlook (pg. 481) | |
Excercises (pg. 481) | |
Further Reading (pg. 486) | |
9. Catalysis (pg. 488) | |
9.1 General Principles of Catalysis (pg. 489) | |
9.2 Forms of Catalysis (pg. 494) | |
9.3 Bronsted Acid-Base Catalysis (pg. 506) | |
9.4 Enzymatic Catalysis (pg. 522) | |
Summary & Outlook (pg. 529) | |
Exercises (pg. 530) | |
Further Reading (pg. 534) | |
10. Organic Reaction Mechanisms, Part 1: Reactions Involving Additions and/or Eliminations (pg. 536) | |
10.1 Predicting Organic Reactivity (pg. 537) | |
10.2 Hydration of Carbonyl Structures (pg. 541) | |
10.3 Electrophilic Addition of Water to Alkenes and Alkynes: Hydration (pg. 544) | |
10.4 Electrophilic Addition of Halides to Alkenes and Alkynes (pg. 547) | |
10.5 Electrophilic Addition of Halogens to Alkenes (pg. 550) | |
10.6 Hydroboration (pg. 553) | |
10.7 Epoxidation (pg. 554) | |
10.8 Nucleophilic Additions to Carbonyl Compounds (pg. 555) | |
10.9 Nucleophilic Additions to Olefins (pg. 566) | |
10.10 Radical Additions to Unsaturated Systems (pg. 568) | |
10.11 Carbene Additions and Insertions (pg. 571) | |
10.12 Eliminations to Form Carbonyls or "Carbonyl-Like" Intermediates (pg. 576) | |
10.13 Elimination Reactions for Aliphatic Systems (pg. 580) | |
10.14 Eliminations from Radical Intermediates (pg. 595) | |
10.15 The Addition of Nitrogen Nucleophiles to Carbonyl Structures, Followed by Elimination (pg. 596) | |
10.16 The Addition of Carbon Nucleophiles, Followed by Elimination -- The Wittig Reaction (pg. 598) | |
10.17 Acyl Transfers (pg. 599) | |
10.18 Electrophilic Aromatic Substitution (pg. 606) | |
10.19 Nucleophilic Aromatic Substitution (pg. 610) | |
10.20 Reactions Involving Benzyne (pg. 611) | |
10.21 The SRN1 Reaction on Aromatic Rings (pg. 614) | |
10.22 Radical Aromatic Substitutions (pg. 614) | |
Summary & Outlook (pg. 616) | |
Exercises (pg. 616) | |
Further Reading (pg. 623) | |
11. Organic Reaction Mechanisms, Part 2: Substitutions at Aliphatic Centers and Thermal Isomerizations/Rearrangements (pg. 626) | |
11.1 Tautomerization (pg. 627) | |
11.2 a-Halogenation (pg. 630) | |
11.3 a-Alkylations (pg. 631) | |
11.4 The Aldol Reaction (pg. 633) | |
11.5 Nucleophilic Aliphatic Substitution Reactions (pg. 636) | |
11.6 Substitution, Radical, Nucleophilic (pg. 667) | |
11.7 Radical Aliphatic Substitutions (pg. 670) | |
11.8 Migrations to Electrophilic Carbons (pg. 673) | |
11.9 Migrations to Electrophilic Heteroatoms (pg. 677) | |
11.10 The Favorskii Rearrangement and Other Carbanion Rearrangements (pg. 681) | |
11.11 Rearrangements Involving Radicals (pg. 682) | |
11.12 Rearrangements and Isomerizations Involving Biradicals (pg. 684) | |
Summary & Outlook (pg. 694) | |
Exercises (pg. 694) | |
Further Reading (pg. 702) | |
12. Organotransition Metal Reaction Mechanisms and Catalysis (pg. 704) | |
12.1 The Basics of Organometallic Complexes (pg. 704) | |
Common Organometallic Reactions (pg. 713) | |
12.3 Combining the Individual Reactions into Overall Transformations and Cycles (pg. 736) | |
Summary & Outlook (pg. 746) | |
Exercises (pg. 747) | |
Further Reading (pg. 749) | |
13. Organic Polymer and Materials Chemistry (pg. 752) | |
13.1 Structural Issues in Materials Chemistry (pg. 753) | |
13.2 Common Polymerization Mechanisms (pg. 778) | |
Summary & Outlook (pg. 799) | |
Exercises (pg. 800) | |
Further Reading (pg. 802) | |
Part III: Electronic Structure Theory and Applications (pg. 804) | |
14. Advanced Concepts in Electronic Structure Theory (pg. 806) | |
14.1 Introductory Quantum Mechanics (pg. 807) | |
14.2 Calculation Methods -- Solving the Schrodinger Equation for Complex Systems (pg. 814) | |
14.3 A Brief Overview of the Implementation and Results of HMOT (pg. 836) | |
14.4 Perturbation Theory -- Orbital Mixing Rules (pg. 843) | |
14.5 Some Topics in Organic Chemistry for Which Molecular Orbital Theory Lends Important Insights (pg. 845) | |
14.6 Organometallic Complexes (pg. 861) | |
Summary & Outlook (pg. 867) | |
Exercises (pg. 867) | |
Further Reading (pg. 874) | |
15. Thermal Pericyclic Reactions (pg. 876) | |
15.1 Background (pg. 877) | |
15.2 A Detailed Analysis of Two Simple Cycloadditions (pg. 877) | |
15.3 Cycloadditions (pg. 892) | |
15.4 Electrocyclic Reactions (pg. 902) | |
15.5 Sigmatropic Rearrangements (pg. 909) | |
15.6 Cheletropic Reactions (pg. 923) | |
15.7 In Summary -- Applying the Rules (pg. 927) | |
Summary & Outlook (pg. 927) | |
Exercises (pg. 928) | |
Further Reading (pg. 932) | |
16. Photochemistry (pg. 934) | |
16.1 Photophysical Processes -- The Jablonski Diagram (pg. 935) | |
16.2 Bimolecular Photophysical Processes (pg. 952) | |
16.3 Photochemical Reactions (pg. 961) | |
16.4 Chemiluminescence (pg. 984) | |
16.5 Singlet Oxygen (pg. 988) | |
Summary & Outlook (pg. 992) | |
Exercises (pg. 992) | |
Further Reading (pg. 998) | |
17. Electronic Organic Materials (pg. 1000) | |
17.1 Theory (pg. 1000) | |
17.2 Conducting Polymers (pg. 1015) | |
17.3 Organic Magnetic Materials (pg. 1021) | |
17.4 Superconductivity (pg. 1029) | |
17.5 Non-Linear Optics (NLO) (pg. 1032) | |
17.6 Photoresists (pg. 1035) | |
Summary & Outlook (pg. 1040) | |
Exercises (pg. 1041) | |
Further Reading (pg. 1043) | |
APPENDIX 1 (pg. 1046) | |
APPENDIX 2 (pg. 1048) | |
APPENDIX 3 (pg. 1050) | |
APPENDIX 4 (pg. 1056) | |
APPENDIX 5 (pg. 1060) | |
APPENDIX 6 (pg. 1074) | |
Index (pg. 1078) | |
Back Cover (pg. 1099) |
Eric V. Anslyn
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
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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