CODE 60828 ACADEMIC YEAR 2022/2023 CREDITS 8 cfu anno 2 CHIMICA E TECNOLOGIA FARMACEUTICHE 8451 (LM-13) - GENOVA SCIENTIFIC DISCIPLINARY SECTOR CHIM/06 LANGUAGE Italian TEACHING LOCATION GENOVA SEMESTER 2° Semester PREREQUISITES Propedeuticità in ingresso Per sostenere l'esame di questo insegnamento è necessario aver sostenuto i seguenti esami: Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) GENERAL AND INORGANIC CHEMISTRY (PHAR)(MD) 55413 2021 ORGANIC CHEMISTRY 60795 2021 Propedeuticità in uscita Questo insegnamento è propedeutico per gli insegnamenti: Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 Pharmaceutical chemistry and technology 8451 (coorte 2021/2022) ORGANIC CHEMISTRY II (PCT)(MD) 60828 2021 TEACHING MATERIALS AULAWEB OVERVIEW The course includes the continuation and deepening of the concepts taught in Organic Chemistry I. The topics covered allow for the acquisition of a more complete view of the basic concepts of organic chemistry. Furthermore, they are largely chosen in such a way as to be preparatory for subsequent courses such as Biochemistry and Pharmaceutical Chemistry. 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. AIMS AND LEARNING OUTCOMES The aim of the Organic Chemistry II course is to provide more advanced concepts of the subject, compared to those learned in the previous Organic Chemistry I course. At the end of the course, the student will have acquired theoretical knowledge on the structure and reactivity of bifunctional compounds, polycyclic aromatic compounds and heterocyclic compounds (aromatic and non-aromatic). They will also have deepened the fundamental strategies for the formation of carbon-carbon bonds and will have learned the basic structures and properties of the main classes of biomolecules. This knowledge is fundamental to face future studies in the biochemical and chemical-pharmaceutical fields. Specifically, the student will be able to: know the main classes of synthetic and natural organic compounds; apply the fundamental rules of the IUPAC nomenclature, in particular in the field of heterocycles; apply basic stereochemical knowledge also to more complex systems; reason critically in order to apply the reactions studied to simple synthetic sequences for the production of required molecules, arguing the choices. PREREQUISITES Basic knowledge of the main topics of organic chemistry. TEACHING METHODS The lessons are given in the traditional way (64 hours in the classroom). The attendance is highly recommended. SYLLABUS/CONTENT 1. FURTHER INSIGHT INTO THE REACTIVITY AND PREPARATION OF BIFUNCTIONAL COMPOUNDS (24 hours, Prof. Ginoble Pandoli) A1 Polyunsaturated and polycyclic systems and bicarboxylic compounds A1.1 Conformations of cycloalkanes and bicycloalkanes A1.1.2 Conformation of fused bicyclic alkanes A1.1.1 Conformations of monocyclic alkanes A1.1.3 Nomenclature and properties of bridged bicyclic systems A1.2 Dienes A1.2.1: Conjugation and UV-visible 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 systems 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 function 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. Riva). B1 Classification and nomenclature of heterocyclic compounds B2 Electronrich aromatic heterocycles B2.1 General features B2.2 Synthesis and reactivity of pyrrole, furan, thiophene and related benzo-fused compounds B3 Electronpoor aromatic heterocycles B3.1 General features B3.2 Synthesis and reactivity of pyridine, quinoline, isoquinoline, pyrimidine, pyrazine, pyridazine B4 Aromatic penta-atomic heterocycles with two heteroatoms B4.1 General features B4.2 Synthesis and reactivity of imidazole, oxazole, isoxazole B5 Saturated strained heterocycles: structure, synthesis and reactivity of oxiranes, 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 Behavior of monosaccharides in acids and in bases C1.1.6 Reduction and oxidation reactions; 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 glycosyl donor). Enzymatic synthesis C1.1.9 Osazones C1.1.10 Kiliani-Fischer synthesis C1.1.11 Ruff and Wohl degradationsC1.1.12 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 Amino acids C3.1 Nomenclature C3.2 Structure and classification C3.3 Acid-base properties C3.4 Isoelectric point C3.5 Synthesis of alpha-amino acids (from alpha-haloacids, from acylaminomalonic esters, through reducing amination, through enantioselective reduction of alpha-acylaminoacrylic acids, through Strecker reaction) C3.6 Resolution of racemic alpha-amino acids C4 Peptides and proteins C4.1 Primary structure, disulfide bonds. C4.2 Protein denaturation C4.3 Determination of primary structure C4.3.1 Through exhaustive hydrolysis coupled with ion exchange chromatography and visualization with ninhydrin C4.3.2 Through Edman method C4.3.3 Through use of cyanogen bromide C4.3.4 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 Sugars C5.3 Nucleosides C5.4 Nucleotides C5.5 Oligonucleotides and Nucleic acids C5.6 Secondary and tertiary structure of DNA C5.7 Examples of genetic mutations RECOMMENDED READING/BIBLIOGRAPHY Chimica Organica AA. VV. a cura di B. Botta Edi-Ermes Chimica Organica di M. Loudon, EdiSES Chimica Organica di J. McMurry, Piccin Chimica Organica di P. Y. Bruice, EdiSES Chimica Organica di P. C. Vollhardt e N. E. Schore, Zanichelli Chimica Organica di W. H. Brown, B. L. Iverson, E. V. Anslyn, C. S. Foote, EdiSES Chimica dei Composti Eterociclici di D. Sica, F. Zollo - EdiSES (l'ultima edizione) Chimica degli Eterocicli di G. Broggini, G. Zecchi – vol. 1 LaScientifica TEACHERS AND EXAM BOARD RENATA RIVA Ricevimento: I'm available every day of the week. Please, contact me one day before by e-mail for an appointment. OMAR GINOBLE PANDOLI Ricevimento: The student reception will take place at the department of Pharmacy (viale Cembrano 4) by appointment, subject to e-mail communication. Exam Board RENATA RIVA (President) OMAR GINOBLE PANDOLI LUCA BANFI (Substitute) LESSONS LESSONS START The lessons will begin February 27, 2023. 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 two members of permanent teaching staff and lasts at least 30 minutes. The students will demonstrate to have reached a sufficient 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 Data Ora Luogo Degree type Note 20/06/2023 09:00 GENOVA Scritto + Orale L'esame si tiene presso il DCCI (Via Dodecaneso, 31). L'aula è visibile sul monitor che si trova all'ingresso. Durante lo scritto è consentito consultare il file "regole nomenclatura per scritto" reperibile su aulaweb esclusivamente in formato cartaceo. 11/07/2023 09:00 GENOVA Scritto + Orale L'esame si tiene presso il DCCI (Via Dodecaneso, 31). L'aula è visibile sul monitor che si trova all'ingresso. Durante lo scritto è consentito consultare il file "regole nomenclatura per scritto" reperibile su aulaweb ma esclusivamente in formato cartaceo. 25/07/2023 09:00 GENOVA Scritto + Orale L'esame si tiene presso il DCCI (Via Dodecaneso, 31). L'aula è visibile sul monitor che si trova all'ingresso. Durante lo scritto è consentito consultare il file "regole nomenclatura per scritto" reperibile su aulaweb ma esclusivamente in formato cartaceo. 04/09/2023 09:00 GENOVA Scritto L'esame si tiene presso il DCCI (Via Dodecaneso, 31). L'aula è visibile sul monitor che si trova all'ingresso. Durante lo scritto è consentito consultare il file "regole nomenclatura per scritto" reperibile su aulaweb esclusivamente in formato cartaceo. L'orale sarà nel pomeriggio del 4 settembre 2023, aula 2 DCCI. 05/09/2023 09:00 GENOVA Orale L'esame si tiene presso il DCCI (Via Dodecaneso, 31). L'aula è visibile sul monitor che si trova all'ingresso. Durante lo scritto è consentito consultare il file "regole nomenclatura per scritto" reperibile su aulaweb esclusivamente in formato cartaceo. L'orale sarà nel pomeriggio del 4 settembre 2023, aula 2 DCCI 19/09/2023 09:00 GENOVA Scritto + Orale L'esame si tiene presso il DCCI (Via Dodecaneso, 31). L'aula è visibile sul monitor che si trova all'ingresso. Durante lo scritto è consentito consultare il file "regole nomenclatura per scritto" reperibile su aulaweb ma esclusivamente in formato cartaceo. 23/01/2024 09:00 GENOVA Scritto + Orale L'esame si tiene presso il DCCI (Via Dodecaneso, 31). L'aula è visibile sul monitor che si trova all'ingresso. Durante lo scritto è consentito consultare il file "regole nomenclatura per scritto" reperibile su aulaweb ma esclusivamente in formato cartaceo. 13/02/2024 09:00 GENOVA Scritto + Orale L'esame si tiene presso il DCCI (Via Dodecaneso, 31). L'aula è visibile sul monitor che si trova all'ingresso. Durante lo scritto è consentito consultare il file "regole nomenclatura per scritto" reperibile su aulaweb ma esclusivamente in formato cartaceo. FURTHER INFORMATION Only the students who have already passed Organic Chemistry 1 are admitted to the exam. The professors will check the observance of this rule just before the written exam.