Overlap Determinant Method in the Theory of Pericyclic Reactions

ISBN-13: 9783540591894 / Angielski / Miękka / 1995 / 126 str.

R. Ponec; Robert Ponec

Opis

The author summarizes the development and the applications of overlap determinant method in various fields of pericyclic reactivity. The greatest advantage of this new method lies in its remarkable simplicity and flexibility owing to which it opens an interesting possibility of the systematic investigation of important mechanistic problems of pericyclic reactivity which were so far beyond the scope of other existing techniques.

Spis treści

1. Introduction.- 2. Pericyclic Reactions.- 2.1 classification.- 3. Woodward-Hoffmann Rules.- 3.1 Correlation Diagrams.- 3.2 Woodward-Hoffmann Rules and Topology.- 4. Frontier Orbital Theory.- 4.1 Substituent Effect in Pericyclic Reactions.- 4.2 Regioselectivity of Pericyclic Reactions.- 4.3 Limitations and Exceptions of Frontier Orbital Theory.- 5. Overlap Determinant Method.- 5.1 Thermal Reactions.- 5.2 Photochemical Reactions.- 5.3 Generalized Overlap Determinant Method.- 6. Least Motion Principle.- 6.1 Similarity Indices.- 6.2 Generalized Similarity Indices.- 6.3 Similarity Indices and the Least Motion Principle.- 7. Mechanisms of Pericyclic Reactions.- 7.1 Concertedness in Pericyclic Reactions.- 7.2 More O Ferrall Diagrams.- 7.3 Topological Criterion of Concertedness.- 7.4 One-step vs. Stepwise Reaction Mechanisms in Pericyclic Reactions.- 7.5 Least Motion Principle and the Mechanisms of Pericyclic Reactions.- 8. Miscelaneous.- 8.1 Evans/Dewar Concept of Aromaticity of Transition States.- 8.2 Electron Correlation in Pericyclic Reactions.- 9. Appendix.- 9.1 Overlap Determinant Method.- 9.2 Topological Density Matrix.- 9.3 Similarity Indices.- 9.4 Second Order Similarity Index.- 10. Future Perspectives.- 11. References.

O autorze

The book is written primarily for students and active research workers in the field of theoretical and physical organic chemistry, who favour the possibility to predict the preferred reaction mechanism or the eventual substituent induced violation of Woodward-Hoffmann rules.