Modern Physical Organic Chemistry"The twentieth century saw the birth of physical organic chemistry - the study of the interrelationships between structure and reactivity in organic molecules - and the discipline matured to a brilliant and vibrant field. Some would argue that the last century also saw the near death of the field. In our opinion, physical organic chemistry is alive and well in the early twenty-first century. New life has been breathed into the field because it has embraced newer chemical disciplines, such as bioorganic, organometallic, materials, and supramolecular chemistries. These newer disciplines have given physical organic chemists fertile ground in which to study the interrelationships of structure and reactivity. Yet, even while these new fields have been developing, remarkable advances in our understanding of basic organic chemical reactivity have continued to appear, exploiting classical physical organic tools and developing newer experimental and computational techniques. Importantly, the techniques of physical organic chemistry and the intellectual approach to problems embodied by the discipline remain as relevant as ever to organic chemistry. Therefore, a course in physical organic chemistry will be essential for students for the foreseeable future. This book is meant to capture the state of the art of physical organic chemistry in the early twenty-first century, and, within the best of our ability, to present material that will remain relevant as the field evolves in the future. A student must know the fundamentals, such as the essence of structure and bonding in organic molecules, the nature of the basic reactive intermediates, and organic reaction mechanisms. However, students should also have an appreciation of the current issues and challenges in the field, so that when they inspect the modern literature they will have the necessary background to read and understand current research efforts. Therefore, while treating the fundamentals, we have wherever possible chosen examples and highlights from modern research areas."--adapted from Preface, page xxiii. |
Contents
PART I | 1 |
Introduction to Structure and Models of Bonding | 3 |
CHAPTER | 7 |
Scaling Electrostatic Surface Potentials | 15 |
Particle in a Box | 21 |
A Brief Look at Symmetry and Symmetry Operations | 29 |
Groups as Perturbations of Allyl | 49 |
CH5Not Really a WellDefined Structure | 55 |
Stereoelectronics in an Acyl Transfer Model | 579 |
Gas Phase Eliminations | 588 |
AconitaseAn Enzyme that Catalyzes Dehydration | 595 |
The Catalytic Triad | 604 |
Summary and Outlook | 617 |
FURTHER READING | 624 |
Enolate Aggregation | 631 |
SUBSTITUTIONS ON ALIPHATIC CENTERS | 637 |
Summary and Outlook | 61 |
CHAPTER 2 | 67 |
How Big is 3 kcalmol? | 93 |
Differing Magnitudes of Energy Values | 100 |
The NMR Time Scale | 106 |
A Conformational Effect on the Material Properties | 116 |
Protein Disulfide Linkages | 123 |
Summary and Outlook | 137 |
FURTHER READING | 143 |
CHAPTER 3 | 149 |
Solvation Can Affect Equilibria | 155 |
A vant Hoff Analysis of the Formation of | 163 |
Summary and Outlook | 201 |
Molecular Recognition | 207 |
Cooperativity in Drug Receptor Interactions | 215 |
The BenesiHildebrand Plot | 221 |
Preorganization and the Salt Bridge | 229 |
CalixarenesImportant Building Blocks for Molecular | 238 |
A Molecular Recognition | 249 |
Summary and Outlook | 292 |
Summary and Outlook | 344 |
FURTHER READING | 350 |
Reactivity Kinetics and Mechanisms | 353 |
Revisiting | 388 |
Realistic Titrations in Water 265 An Organometallic Example of Using the | 395 |
The Role | 401 |
Summary and Outlook | 413 |
CHAPTER 8 | 414 |
Thermodynamics and Kinetics | 421 |
Stereoisomerism and Connectivity 300 The Use of Primary Kinetic Isotope Effects to Probe | 425 |
Chiral Shift Reagents 308 The Use of an Inverse Isotope Effect to Delineate | 431 |
Controlling Polymer TacticityThe Metallocenes 332 Using Fractionation Factors to Characterize Very Strong | 439 |
Catalytic Antibody | 450 |
Where TST May be Insufficient 374 Nucleophilic Assistance in the Solvolysis of Arylvinyl | 459 |
Applying the Principle of Microscopic Reversibility Insight into Transition State Structures | 465 |
Molecularity vs Mechanism Cyclization Reactions and An Example of an Unexpected Product | 472 |
or Trap a Proposed Intermediate | 473 |
Determination of 14Biradical Lifetimes Using | 480 |
Summary and Outlook | 482 |
Catalysis | 489 |
The Application of Figure 9 4 to Enzymes | 494 |
Toward an Artificial Acetylcholinesterase | 501 |
A Model for GeneralAcidGeneralBase Catalysis | 514 |
Cyclodextrins Lead the Way | 530 |
Organic Reaction Mechanisms Part | 537 |
CHAPTER 10 | 539 |
Cyclic Forms of Saccharides and Concerted Proton | 545 |
Mechanisms of Asymmetric Epoxidation Reactions | 558 |
Natures Hydride Reducing Agent | 566 |
The Captodative Effect | 573 |
ELIMINATIONS | 576 |
Gas Phase SN2 ReactionsA Stark Difference in Mechanism | 641 |
Contact Ion Pairs vs SolventSeparated Ion Pairs | 647 |
Carbocation Rearrangements in Rings | 658 |
Further Examples of Hypervalent Carbon | 666 |
Brominations Using NBromosuccinimide | 673 |
ISOMERIZATIONS AND REARRANGEMENTS | 674 |
Femtochemistry and Singlet Biradicals | 693 |
Summary and Outlook | 695 |
FURTHER READING | 703 |
CHAPTER 12 | 709 |
Electrophilic Aliphatic Substitutions SE2 and SE1 | 715 |
CH Activation Part I | 722 |
Summary and Outlook | 747 |
Organic Polymer | 753 |
Monodisperse Materials Prepared Biosynthetically | 756 |
Protein Folding Modeled by a TwoState Polymer | 762 |
Dendrimers Fractals Neurons and Trees | 769 |
SelfAssembling Monolayers | 778 |
FreeRadical Living Polymerizations | 787 |
PMMAOne Polymer with a Remarkable Range | 793 |
Summary and Outlook | 800 |
Electronic Structure Theory and Applications | 805 |
Advanced Concepts in Electronic | 807 |
MethaneMolecular Orbitals or Discrete Single | 827 |
ThroughBond Coupling and Spin Preferences | 861 |
Summary and Outlook | 868 |
FURTHER READING | 875 |
CHAPTER 15 | 887 |
Allowed Organometallic 2+2 Cycloadditions | 895 |
Electrocyclization in Cancer Therapeutics | 910 |
The OxyCope | 921 |
EXERCISES | 929 |
Photochemistry | 935 |
CHAPTER 16 | 937 |
Physical Properties of Excited States | 944 |
Isosbestic PointsHallmarks of OnetoOne Stoichiometric | 949 |
Sensitization | 956 |
SingleMolecule FRET | 961 |
TransCyclohexene? | 967 |
Summary and Outlook | 993 |
FURTHER READING | 999 |
CHAPTER 17 | 1011 |
Scanning Probe Microscopy | 1040 |
Summary and Outlook | 1041 |
Conversion Factors and Other Useful Data | 1047 |
The Organic Structures of Biology | 1057 |
How to Denote Resonance | 1064 |
Pushing Electrons for Radical Reactions | 1071 |
1079 | |
Common terms and phrases
acid activation addition alkene analysis associated atoms base becomes binding called carbon carbonyl catalysis cation Chapter charge Chem chemical chemistry common complex compounds concentration conformation Connections consider constant coordinate create dependence deprotonation described determined developed discussed effect electron elimination energy equation equilibrium examine example Figure force formation function given gives Hence hydrogen bond important increases interaction intermediate involved isotope kcal/mol kinetic leads leaving group less ligand lone pair lower means mechanism metal method mixing molecular molecule nature negative Note nucleophile observed occurs orbitals organic pair polar polymer polymerization positive possible potential predict proton quantum mechanical radical reactant reaction reactive reference relative resonance ring shown shows similar simple solution solvent species stability step stereoisomers strain structure substitution surface Table temperature term theory tion transition values