AIMS AND CONTENT

LEARNING OUTCOMES

Further insight into the reactivity of organic molecules through the study of difunctional molecules. Carbon-carbon bond forming reactions with particular emphasis on the costruction of cyclic systems. Heterocycles. Natural organic substances.

TEACHING METHODS

The lessons are given in the traditional way (64 hours in the classroom). The attendance is compulsory. Only those students who have attended at least 60% of the lessons are admitted at the exam.

SYLLABUS/CONTENT

1. FURTHER INSIGHT INTO THE REACTIVITY AND PREPARATION OF BIFUNCTIONAL COMPOUNDS (24 hours, Prof. Banfi)
   • A1 Polyunsaturated and polycyclic systems and bicarboxylic compounds
     • A1.1 Conformations of cycloalkanes and bicycloalkanes
       • A1.1.1 Conformations of monocyclic alkanes
       • A1.1.2 Conformation of fused bicyclic alkanes
       • A1.1.3 Nomenclature and properties of bridged bicyclic systems
     • A1.2 Dienes
       • A1.2.1: Conjugation and UV-visble absorption
       • A1.2.2: Electrophilic addition to conjugated dienes
       • A1.2.3: Pericyclic cycloadditions: the Diels-Alder reaction
       • A1.2.4 Ring-closing metathesis
       • A1.2.5 Allenes
     • A1.3 Bicarboxylic acids
     • A1.4 Aromatic polycyclic ystems
       • A1.4.1: Nomenclature and properties
       • A1.4.2: Fullerenes, graphite, graphene, carbon nanotubes
       • A1.4.3: Arene oxides
       • A1.4.4: Electrophilic substitutions on naphthalene
     • A1.5 Biaryl systems
       • A1.5.1 Chirality in biaryls
       • A1.5.2 Suzuki reaction for the synthesis of biaryls and dienes
   • A2 Compounds with two oxygenated functions or one oxygenated functiona and an unsaturation
     • A2.1 Conjugated carbonyl and carboxylic compounds
       • A2.1.1 Preparation through: halogenation/elimination, crotonic condensation, Knoevenagel reaction; intramolecular metathesis; Wittig and Horner-Wadsworth-Emmons reactions
       • A2.1.2 Synthetic equivalence
       • A2.1.3 Conjugated nucleophilic additions: reactions with mild nucleophiles, with organometallic reagents, with hydrides, Michael reaction.
       • A2.1.4 Robinson annulation
       • A2.1.5 Conjugated additions in biology
       • A2.1.6 Conjugated additions and other reactions of enamines
     • A2.2 1,3-Dioxygenated compounds
       • A2.2.1: Cross aldol reactions with enolate preformation
       • A2.2.2: Cross alsol reactions with synthetic equivalents of aldehydes
       • A2.2.3 Oxidations with diacetoxyiodobenzene and Swern oxidation
       • A2.2.4 Claisen and Dieckmann condensations
       • A2.2.5 Aldol additions and Claisen condensations in biology
     • A2.3 1,2-Dioxygenated compounds
       • A2.3.1 Retrosynthetic strategies: logical and illogical disconnections
       • A2.3.2 Cyanide anion as acyl anion equivalent
       • A2.3.3 Isocyanides: Passerini reaction
       • A2.3.4 Dithianes
       • A2.3.5 1,2-Diols
       • A2.3.6 Cyclic acetals
   • A3) Radical reactions, phenols, quinones
     • A3.1 Radical reactions
       • A3.1.1: Generality
       • A3.1.2: Radical polymerizations
       • A3.1.3 Autooxidations
       • A3.1.4 Anti-oxidants
     • A3.2 Phenols as natural anti-oxidants
     • A3.3 Quinones
2. HETEROCYCLIC COMPOUNDS (21 h, Prof. Petrillo).
   • Classification and nomenclature of heterocyclic compounds
   • Electronrich aromatic heterocycles
     • General features
     • Synthesis and reactivity of pyrrole, furan, thiophene and related benzo-fused compounds
   • Electronpoor aromatic heterocycles
     • General features
     • Synthesis and reactivity of pyridine, quinoline, isoquinoline,pyrimidine, pyrazine, pyridazine
   • Aromatic penta-atomi heterocycles with two heteroatoms
     • General features
     • Synthesis and reactivity of imidazole, oxazole, isoxazole
   • Saturated strained heterocycles: structure, synthesis and reactivity of oiranes, aziridines, oxetanes, azetidines
3. BIOMOLECULES (19 h, Prof. Riva).
   • C1 Carbohydrates
     • C1.1 Monosaccharides
       • C1.1.1 Stereochemical families
       • C1.1.2 Fischer and Haworth formulas, pyranose and furanose conformations
       • C1.1.3 Anomeric effect
       • C1.1.4 Mutarotation
       • C1.1.5 Behaviour of monosaccharides in acids and in bases
       • C1.1.6 Reduction and oxidation reactons; reducing sugar assays
       • C1.1.7 Glycosides: structure, properties and synthesis of simple glycosides
       • C1.1.8 Synthetic strategies for the synthesis of complex glycosides through chemical means (use of protecting groups and activation of glycosy donor). Enzymatic synthesis
       • C1.1.9 Osazones
       • C1.1.10 Kiliani-Fischer synthesis
       • C1.1.11 Ruff and Wohl degradations
       • C1.1.12 Determination of relative and absolute configuration of main monosaccharides
     • C1.2 Disaccharides: maltose, cellobiose, saccharose and lactose
     • C1.3 Polysaccharides: structure and properties of main polysaccharides (starch, glycogen, cellulose, chitin, pectin, hyaluronic acid)
     • C1.4 Antigene determinants of cells; blood groups
     • C1.5 Glycoconjugates
       • C1.5.1 glycolipids
       • C1.5.2 glycoproteins
   • C2 Lipids
     • C2.1 Fatty acids and derivatives (amides, waxes)
     • C2.2 Eicosanoides (prostaglandins etc.)
     • C2.3 Glycerolipids (triglycerides: fats, oils)
     • C2.4 Soaps and tensioactive compounds
     • C2.5 Glycerophospholipids
     • C2.6 Sphingolipids
     • C2.7 Terpenes, Terpenoids and their biosynthesis
     • C2.8 Steroids
   • C3 Amminoacids
     • C3.1 Nomenclature
     • C3.2 Structure and classification
     • C3.3 Acid-base properties
     • C3.4 Isoelectric point
     • C3.5 Synthesis of alpha-aminoacids (from alpha-haloacids, from acylaminomalonic esters, through reducing amination, through enantioselective reduction of alha-acylaminoacrylic acids, through Strecker reaction)
     • C3.6 Resolution of racemic alpha-amminoacids
   • C4 Peptides and proteins
     • C4.1 Primary structure, secondary structure (alpha-helix, beta-sheet, random coil), tertiary and quternary structure
     • C4.2 Protein denaturation
     • C4.3 Determination of primary structure
       • Through exhaustive hydrolysis coupled with ion exchange chromatography and visualization with ninhydrin
       • Through Edman method
       • Through use of cyanogen bromide
       • Through enzymatic methods
     • C4.4 Chemical synthesis in solution (from left to right and from right to left; use of protecting groups; activation of carboxylic function) and in solid phase (Merrifield resins)
   • C5 Nucleic acids
     • C5.1 Nitrogen bases
     • C5.2 ZSugars
     • C5.3 Nucleosides
     • C5.4 Nucleotides
     • C5.5 Oligonucleotides and Nucleic acids
     • C5.6 Secondary and tertiary structure of DNA
     • C5.7 Examples ofgenetic mutations

RECOMMENDED READING/BIBLIOGRAPHY

• Chimica Organica AA. VV. a cura di B. Botta Edi-Ermes 2011 (p. 1174)
• Chimica Organica di Marc Loudon, EdiSES 2010 (p. 1374)
• Chimica Organica di McMurry, Piccin 2012 (p. 1262)
• Chimica dei Composti Eterociclici di D. Sica, F. Zollo - EdiSES (l'ultima edizione)
• Chimica degli Eterocicli di G. Broggini, G. Zecchi – vol. 1 LaScientifica (l'ultima edizione)

TEACHERS AND EXAM BOARD

Exam Board

LUCA BANFI (President)

GIOVANNI PETRILLO (President)

RENATA RIVA (President)

LISA MONI

CINZIA TAVANI

LESSONS

LESSONS START

The lessons will begin february 20, 2017.

Class schedule

ORGANIC CHEMISTRY II (PCT)(MD)

EXAMS

EXAM DESCRIPTION

There will be a preliminary written exam consisting in 12 questions. The students will have 90 minutes for answering. The written exam will be followed, the same day, by an oral exam. At least one question for each of the three parts will be asked at the oral. Only the students who get a sufficient grade at the written exam will be admitted to the oral. The oral exam must be given the same day than the written one and if a student fails to pass the oral, will have to repeat also the written part. In general, the grade of the written exam in not influential on the final vote. Only in particular cases, when the written exam has a very high mark, it can positively influence the final grade.

ASSESSMENT METHODS

The oral exam is always carried out by three members of permanent teaching staff and lasts at least 45 minutes (15 minutes for each professors). The students will demonstrate to have reached a suffidient knowledge both by answering to questions, and by drawing at the blackboard formulas, reaction equations, mechanisms and so on. Therefore, also taking into account the preliminary written part, the commission is definitely able to verify, with high accuracy, the fullfilment of learning outcomes. If the commission decides that the learning outcomes have not been met, the student will be invited to try again the exam in a following date.

Exam schedule

FURTHER INFORMATION

Only the students who have already passed Organic Chemistry are admitted to the exam. The professors will check the observance of this rule just before the written exam.