The main objective of the course is to provide an information about the relationship between the structure of organic compounds and their chemical reactivity. Different ways of chemical activation and the courses of the ractions are discussed.
1. Structure and reactivity relationship. Calibration points in chemistry. Inner parameters of the structure and its deformations. Physical properties caused by (a) geometry of nuclei, (b) electron density and its change. Activation and driving force of the chemical reactions.
2. Theory of molecular orbitals. Hückel approximation.
3. Stability of molecules. Thermodynamic additive calculations. Conformations of acyclic and cyclic hydrocarbons. Heteroatom effects. Hyperconjugation. Anomeric effect.
4. Aromaticity a antiaromaticity. Aromatic ions and dipoles. Aromaticity of the transition state in the pericyclic reactions.
5. Non-covalent interactions and solvent effects. Solutions. Hughes-Ingold principles. H-bonding. Hydrophobic effect. Molecular recognition.
6. Proton transfer. Acid-base equilibria.
7. Chemical kinetics and reactivity. HSAB. Nucleophiles and electrophiles. Rate constants. Hammond and Curtin-Hammond principles. Driving force of the reactions.
8. Thermodynamics and kinetics - the tools to study chemical reactions. LFER. Hammett equation. Taft equation. QSAR. Kinetic isotope effects. Entropy vs. enthalpy.
9. Catalysis. Transition metal catalysis. Heterogeneous catalysis. Enzymatic catalysis. Brönsted catalysis.
10. Electron transfer. Marcus equation.
11. Photochemistry and photophysics.
12. Non-classical activation of chemical reactions. Spin chemistry. Magnetic field effects. Microwave chemistry. Sonochemistry.
E. V. Anslyn, D. A. Dougherty: Modern Physical Organic Chemistry. University Science Books, Kausalito, California 2005. ISBN 1-891389-9
O. Exner: Korelační vztahy v organické chemii. SNTL, Praha 1981
O. Exner: Struktura a fyzikální vlastnosti organických sloučenin. SNTL, Praha 1985.
I. Fleming: Hraniční orbitaly a reakce v organické chemii. SNTL, Praha 1983.
F. A. Carey, R. J. Sundberg: Advanced Organic Chemistry, 3rd edition, Part A: Structure and Mechanisms. Plenum Press, New York, 1993.