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Lecturer(s)
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Hanusek Jiří, prof. Ing. Ph.D.
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Váňa Jiří, doc. Ing. Ph.D.
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Course content
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1. Chemical bond and structure. Hybridization and its transitions. Aromaticity: Classical and non-classical aromates/ heteroaromates, charged aromates. Homoaromaticity and antiaromaticity. Polar effects. 2. Molecular orbitals theory. Pericyclic and electrocyclic reactions. Woodward-Hoffmanno rules. Cycloadditions and sigmatropic rearrangements. 3. Photochemistry and photocatalysis. Jablonski diagrame. Luminiscence. Protecting groups. DFT methods. Calculations of energetic reaction profiles, influence of solvent molecules. 4. Basic principles of stereochemistry. Types of chirality in organic molecules - chirality on atom, helicity, axial chirality, atropoisomerism. Chirality and prochirality in molecular spectra, racemates, racemization, separation of enantiomers, preparation of optically pure compounds. Conformation. 5. Basic mechanistic principles: kinetic and thermodynamic control, Hammond postulate, Hammett-Curtinův principle, Bell-Evans-Polanyi principle. Stability and reactivity. 6. Nucleophilic substitution on sp3 carbon. Frontier mechanisms. Factors influencing nucleophilic substitution (substituents, solvent, structure of substrate and nucleophile, catalysis, stereochemistry). Mechanistic criterions. 7. Nucleophilic substitution on vinylic sp2 carbon. Frontier mechanisms. Factors influencing nucleophilic substitution (substituents, solvent, structure of substrate and nucleophile, catalysis, stereochemistry). Mechanistic criterions. 8. Nucleophilic substitution on carbonyl sp2 carbon. Frontier mechanisms. Factors influencing nucleophilic substitution (substituents, solvent, structure of substrate and nucleophile, catalysis, stereochemistry). Mechanistic criterions. 9. Electrophilic aromatic substitution. Kinetic equation and its limit cases, catalysis, kinetic isotope effect. Examples of SEAr. 10. Electrophilic rearrangements on aromates. 11. Electrophilic additions and eliminations. Frontier mechanisms, regioselectivity and stereochemistry. 12. Oxidations (alkenes, alcohols, carbonyl compounds, nitrogen and sulfur compounds) and reductions with complex hydrides, diborane, metals and catalytic hydrogenations (homo- and heterogeneous). 13. Radical additions and substitutions. Structure and stability of radicals, charged radicals. Spectral identification of radicals.
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Learning activities and teaching methods
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Monologic (reading, lecture, briefing)
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Learning outcomes
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The aim of the course is to acquaint students with the detailed mechanisms of reactions of organic compounds and to relate them to the physico-chemical experiments that are used to design them. After completing the course, the student will be able to theoretically evaluate the effects of structure and environment on the reactivity of organic compounds and to design (and also to perform a model optimization) a reaction mechanism.
After completing the course, the student will be able to understand the reaction mechanisms of organic reactions and other laws that affect them. Furthermore, he will be able to competently design the structure of starting materials and reaction conditions so that the result of the reaction would be clearly predictable.
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Prerequisites
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Study courses: Organic chemistry and Basic of organic synthesis.
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Assessment methods and criteria
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Oral examination, Written examination
The examination involves writing and oral part. Writing part involving tasks from subject must be accomplished before oral part (least 50% of possible points) whose result will be included in the whole classification of the subject. The main exam is oral and the topic of the exam involves discussion concerning selected reaction mechanisms, the possibilities of their proving or disproving.
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Recommended literature
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Carey F.A., Sundberg R.J.:. Advanced Organic Chemistry, Part A: Structure and Mechanisms, 3rd Ed., Plenum Press, New York 1990..
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Foresman, James B. Exploring chemistry with electronic structure methods. Pittsburgh: Gaussian, 1996. ISBN 0-9636769-3-8.
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Isaacs N.:. Physical Organic Chemistry, 2nd Ed., Logman Scientific Technical, Wiley, New York, 1995..
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March J.:. Advanced Organic Chemistry, Reactions, Mechanisms and Structure, 4th Ed., Wiley, New York, 1992..
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