Provide the competences to understand the reaction mechanism (and stereochemistry) of the most common organic reactions and propose at least one synthesis for a selected organic compound.
Prerequisites
Inorganic Chemistry and
Organic Chemistry I
Teaching Methods
Blackboard and slides will be used.
Type of Assessment
Oral exam.
Course program
ORGANIC CHEMISTRY II (CTF – 1st Semester – 9 CFU)
Prof. Cristina Nativi (cristina.nativi@unifi.it)
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.
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)