B016523 - ORGANICA CHEMISTRY II

Italian

Study and description of organic reaction mechanisms. Hammond’s postulate and Curtin-Hammett principle. Substituent effects and linear free-energy relationships. Solent effect. Advanced sterechemical principles. Diols, bicarboxylic acids, hydroxyl-acids, -esters, aldehyde, ketones. Lactones and lactames. Bidentate species. HSAB theory. Rearragement reactions. Pericyclic reactions. Aminoacids and carbohydrates. Sharpless epoxidation. Swern oxidation. Birch reduction. Heterocycles.

G.M. Loudon Organic Chemistry Oxford
Smith&March Advanced Organic Chemistry Wiley
Carey&Sundeberg Advanced Organic Chemistry Plenum Press

Acquisition of credits for:
Inorganic Chemistry
Organic Chemistry I

The course is delivered using the blackboard and taking advantage of slides. Students are provided with a copy of the slides.

Reaction mechanisms and reactivity
Kinetic and thermodynamic (main concepts). Reaction controlled by kinetic or thermodynamic. Transition state, activation energy, principle of Hammond and Curtin-Hammett equation.
Free energy correlations. Hammett equation. Brown sigma. Taft equation.
Solvent effect. Supercritical solvents.
Stereochemistry:
Prochirality. Omo-, enantio- and diasterotopicity. Chiral auxiliaries. Asimmetric induction. Cram and Felkin-Ahn models. Mitzunobu reaction.
Reactions controlled by orbital symmetry
Molecular orbitals and frontiers MO. Electrocyclic reactions, chelotropic and sigmatropic reactions. Cycloadditions 2+2 and 4+2. Diels-Alder reactions: direct and inverse.
Rearrangements:
Anionotropic, cationotropic and radical rearrangements: characteristic and stereochemistry. Rearrangements of: Wagner-Meerwein, Wolff, Hoffmann, Curtius, Schmidt, Bayer-Villiger, Wittig, Stevens, Favorskii, benzidic rearrangement.
Bifunctional and polyfunctional compounds
1,2-diols. Sharpless epoxidation. Bicarboxylic acids. Oxiacids. Alpha, beta-insaturated derivatives (carbonyls, carboxyls, acids, nitriles). Bidentate derivatives: reactivity and properties. Michael reaction and Robinson anellation reaction.
Carbohydrates: properties, classification and stereochemistry. D and L series, anomeric effect, mutarotation, open chain and cyclic structure of the most common monosaccharides. Kiliani-Fisher reaction, oxidation and redaction. Metylation and acetylation of monosaccharides. Glycosides (generalities). Disaccharides: maltose, lactose and saccharose. Polysaccharides: starch and cellulose. Nucleosides and nucleotides.
Aminoacids: properties, acidity, solubility. Acid and basic AA. Isoelectric point. Peptides and proteins. Synthesis of peptides. Solid phase synthesis.
Polynuclear aromatic compounds
Naphtalene, antracene and fenantrene: SEAr and aromaticity.
Heterocyclic compounds:
Nomenclature and properties. Aromatic heterocycles. General reactivity. Pyridine and amminopyridine, pyrrole, tiophene and furan. Azoles.
Oxidations and reductions
Reduction with hydrides: stereoselective and regioselective. 9-BBN, Alpine borane, selectrides. Birch reduction. Wilkinson reduction. Swern oxidation.
Examples of organometallic reactions (Heck, Sonogashira, Suzuky)