| Topic 1. Mechanisms of organic reactions |
Introduction: reaction mechanisms, transition state, activation energy. Thermodynamic and kinetic control. Effect of solvent. Hammond postulate, Curtin-Hammett principle. Determination of reaction mechanisms. Effect of substituents: Hammett equation. Isotope effects. Acid and base catalysis. Characterization of intermediates. |
| Topic 2. Pericyclic reactions. |
Frontier orbital theory. Woodward and Hoffmann rules. Cycloadditions: Diels-Alder reaction, [2 + 2], [3 + 2]. Sigmatropic rearrangements: Claisen, Cope, [2,3], [1, n], ene, cheletropic. Electrocyclic reactions. |
| Topic 3. Radicals and carbenes. |
Structure. Preparation of radicals. Radical reactions: coupling, addition, fragmentation and transpositions. Formation of C-C inter- and intramolecular. Radical formation induced by metals. Carbenes. Diazomethane. Carbenes types. Reactions of carbenes: insertion into C-H bonds, rearrangements, metathesis. |
| Topic 4. Photochemical reactions. |
General principles. Photochemistry and orbital structure. Photochemistry of carbonyl compounds, alkenes and dienes, and aromatics. |
| Topic 5. Synthetic methods and applications. |
Introduction. Protecting groups. Synthetic equivalents. Retrosynthetic analysis: disconnections, chemoselectivity, functional group interconversion. Asymmetric synthesis, chiral pool, auxiliaries and chiral reagents, asymmetric catalysis. Examples. |
Subjects