The Conservation of Orbital Symmetry

The Conservation of Orbital Symmetry examines the principle of conservation of orbital symmetry and its use. The central content of the principle was that reactions occur readily when there is congruence between orbital symmetry characteristics of reactants and products, and only with difficulty when that congruence does not obtain—or to put it more succinctly, orbital symmetry is conserved in concerted reaction. This principle is expected to endure, whatever the language in which it may be couched, or whatever greater precision may be developed in its application and extension.
The book opens with a review of the elementary aspects of the molecular orbital theory of bonding. This is followed by separate chapters on correlation diagrams, the conservation of orbital symmetry, theory of electrocyclic reactions, theory of cycloadditions and cycloreversions, and theory of sigmatropic reactions. Subsequent chapters deal with group transfers and eliminations; secondary conformational effects in concerted cycloaddition reactions; and generalized selection rules for pericyclic reactions.

1. Introduction

2. Orbitals and Bonding

3. Correlation Diagrams

3.1. General Comments on the Construction of Correlation Diagrams

3.2. Precautions in the Construction of Correlation Diagrams

4. The Conservation of Orbital Symmetry

5. Theory of Electrocyclic Reactions

5.1. Electrocyclic Reactions Exemplified

6. Theory of Cycloadditions and Cycloreversions

6.1. Cycloadditions and Cycloreversions Exemplified

6.2. [2+2] Cycloadditions in the Photochemistry of the Cyclohexadienones and Cyclohexenones

6.3. The [2+2+2] Cycloaddition Reaction Prismane

6.4. [2+2+2+2] Cycloadditions

7. Theory of Sigmatropic Reactions

7.1. Sigmatropic Reactions Exemplified

7.2. Sequential Sigmatropic Shifts

8. Group Transfers and Eliminations

9. Secondary Effects

10. Divertissements!

10.1. Cheletropic Reactions

10.2. Cycloaddition Reactions of Ketenes

11. Generalized Selection Rules for Pericyclic Reactions

12. Violations

13. Other Theoretical Work

14. Conclusion