Orbital Symmetry and Reaction Mechanism: The OCAMS View [Paperback]

Criteria of orbital symmetry conservation had a profound influence on mechanistic thinking in organic chemistry and are still commonly applied today. The author presents a coherent set of operational rules for the analysis of scope and reliability. It is written from the viewpoint of Orbital Correspondence Analysis in Maximum Symmetry (OCAMS). Its advantage lies in its provision of a coherent overview of the relation between symmetry and mechanism. For reasons of consistency, the book remains within the framework of molecular orbital theory.Criteria of orbital symmetry conservation had a profound influence on mechanistic thinking in organic chemistry and are still commonly applied today. The author presents a coherent set of operational rules for the analysis of scope and reliability. It is written from the viewpoint of Orbital Correspondence Analysis in Maximum Symmetry (OCAMS). Its advantage lies in its provision of a coherent overview of the relation between symmetry and mechanism. For reasons of consistency, the book remains within the framework of molecular orbital theory.I. Preliminary Survey.- 1. The Woodward-Hoffmann Rules in Perspective.- 1.1 Prolegomenon.- 1.2 The Suprafacial-Antarafacial Dichotom.- 1.2.1 Ground-State Reactions.- 1.2.2 Excited State Reactions.- 1.3 Frontier Electrons and Frontier Orbitals.- 1.3.1 HOMO-LUMO Interactio.- 1.3.2 Superjacent and Subjacent Orbitals.- 1.4 Orbital and Configuration Correlation.- 1.4.1 Frontier Electron Energy.- 1.4.2 Correlation of Electron Configurations.- 1.4.2.1 [4+2]-Cycloaddition and Cycloreversion.- 1.4.2.2 [2+2]-Cycloaddition and Cycloreversion.- 1.5 Problems and Prospects.- 1.5.1 Some Unanswered Questions.- 1.5.2 Where Do We Go From Here?.- 1.6 References.- II. Symmetry and Energy.- 2. Atoms and Atomic Orbitals.- 2.1 Is an Isolated Atom Spherically Symmetrical?.- 2.2 Desymmetrization by an External Field.- 2.2.1 p Orbitals in a Magnetic Field.- 2.2.2 p Orbitals in a Quadrupolar Field.- 2.2.3 Digression: Solă&