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B016523 - ORGANICA CHEMISTRY II
Main information
Teaching Language
Suggested readings
Learning Objectives
Prerequisites
Teaching Methods
Type of Assessment
Course program
Academic Year 2017-18
Course year
Third year - First Semester
Belonging Department
Chemistry "Ugo Schiff"
Course Type
Single education field course
Scientific Area
CHIM/06 - ORGANIC CHEMISTRY
Credits
9
Teaching Hours
72
Teaching Term
25/09/2017 ⇒ 30/04/2019
Attendance required
Yes
Type of Evaluation
Final Grade
Course program
show
Lectureship
Teaching Language
Italian
Suggested readings (Search our library's catalogue)
G.M. Loudon Organic Chemistry Oxford
Smith&March Advanced Organic Chemistry Wiley
Carey&Sundeberg Advanced Organic Chemistry Plenum Press
Smith&March Advanced Organic Chemistry Wiley
Carey&Sundeberg Advanced Organic Chemistry Plenum Press
Learning Objectives
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
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.
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)
Bibliogaphy
G.M. Loudon Organic Chemistry Oxford
Smith&March Advanced Organic Chemistry Wiley
Carey&Sundeberg Advanced Organic Chemistry Plenum Press
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.
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)
Bibliogaphy
G.M. Loudon Organic Chemistry Oxford
Smith&March Advanced Organic Chemistry Wiley
Carey&Sundeberg Advanced Organic Chemistry Plenum Press