Unit ORGANIC CHEMISTRY II
- Course
- Chemistry and technology of drugs
- Study-unit Code
- 65005311
- Curriculum
- In all curricula
- Teacher
- Andrea Temperini
- Teachers
-
- Andrea Temperini
- Hours
- 162 ore - Andrea Temperini
- CFU
- 11
- Course Regulation
- Coorte 2020
- Offered
- 2022/23
- Learning activities
- Base
- Area
- Discipline chimiche
- Academic discipline
- CHIM/06
- Type of study-unit
- Obbligatorio (Required)
- Type of learning activities
- Attività formativa monodisciplinare
- Language of instruction
- Italian
- Contents
- Carbohydrates. Structure and nomenclature. Chemistry of carbohydrates.Heterocyclic chemistry. Nomenclature. Systematic (Hantzsch-Widman) nomenclature. Aromatic and nonaromatic heterocycles. Symthesis of pyrrole, pyridine, quinoline, indole. Cyclization reactions and Cycloaddition reactions in ring synthesis.Concepts of Organic synthesis. Conformation and Stereochemistry. Methods of ring formations: Diels-Alder reaction; Annelation methods; Ring Closure Reactions; Ring Formation via Polyene Cyclization.Preparation of small rings. Synthetically useful rearrangements. Organometallic chemistry. Alkylation of Enolates and Other Carbon Nucleophiles. Hydration methods. Hydroxylation Methods. Reductions. Oxidation. Halogenation. Preparation of Alkenes. peptide synthesis. Some laboratory experiments to acquire the laboratory techniques and bibliography research.
- Reference texts
- Copies of slides on Unistudium Platform.Consultation texts:Advanced Organic Chemistry, 4th Ed., Part A and BFrancis A. Carey and Richard J. SundbergKluwer Academic / Plenum Publishers, New York March's Advanced Organic Chemistry, 6th Ed.Michael B. Smith and Jerry MarchJohn Wiley & Sons Inc., New York Organic Synthesis - Strategy and ControlP. Wyatt, S. WarrenJohn Wiley & Sons, Ltd, Chichester, England Basic Organic StereochemistryErnest L. Eliel, Samuel H. Wilen, Michael P. DoyleJohn Wiley & Sons Inc., New York Heterocyclic ChemistryT. L. GilchristLongman Scientific & Technical, Harlow (England) Strategic Applications of Named Reactions in Organic SynthesisL. Kurti, B. CzaboElsevier Academic Press Name Reactions (II Edition)A Collection of Detailed Reaction MechanismsJie Jack LiSpringer, Berlin
- Educational objectives
- The main aim of this teaching is to provide students with the bases needed to address the synthesis of a target molecule with moderate complexity. Main knowledge acquired will be:- understand the various possibilities for the functional group interchanges;- incorporate in the synthetic strategy the newest methodologies for transition metal-catalyzed reactions and synthesys of carbocycles and heterocycles;- evaluate the use of chiral induction towards stereoselective synthesis of compounds;- analysis of a molecular structure and critical evaluation of the solution founded for its synthesis;The main competence will be:- provide a reasoned synthesis of a molecular target based on existing synthetic knowledge;- discuss on the advantages and disadvantages of the use of different reagents in standard organic synthesis;- identify the concepts and principles of organic synthesis and evaluate new metodological trends for the efficient synthesis of bioactive molecules;
- Prerequisites
- In order to be able to understand and apply the majority of the chemical reactions described within the Course, it is necessary to have successfully passed the Organic Chemistry I exam. Moreover, due to the new topics introduced, knowledge of the principal organic reaction mechanisms represents a mandatory prerequisite for the student planning to follow this course with profit.
- Teaching methods
- The course is organized as follows:- lectures on all subjects of the course;- practical training at the organic synthesis laboratory. Students will perform single-seat exercises concerning the basic techniques of an organic chemistry laboratory and some simple organic reactions.
- Other information
- Attendance is mandatory
- Learning verification modality
- The exam consists on an oral test that consists on an interview of about 60 minutes long aiming to ascertain the knowledge level and the understanding capability acquired by the student on theoretical and methodological contents as indicated on the program. The oral exam will also test the student communication skills and his autonomy in the organization and exposure of the theoretical topics. Moreover, there is no exam for practical training at the organic synthesis laboratory but only e brief test concerning the practical skills acquired during the laboratory activity
- Extended program
- CARBOHYDRATES: name and structure of carbohydrates, the polyfunctional chemistry of sugars; construction and progressive degradation of sugars: evidence of the structure of aldoses.
PROTECTION AND DEPROTECTION OF THE MAIN FUNCTIONAL GROUPS: alcohols, diols, amines, aldehydes and ketones, acids.
SYNTHESIS OF OLIGOPEPTIDES IN SOLID PHASE: amino acids and their protection, activation of the carboxyl group, and coupling. Deprotection and elongation of the peptide chain.
HETEROCYCLIC COMPOUNDS: nomenclature: rules of the Hantzsch-Widman systematic nomenclature and substitute nomenclature; classification of heterocyclic compounds. [4 + 2] and 1,3-dipolar cycloaddition and cyclization reactions (Baldwin rules) in the preparation of heteroarocyclic compounds. Synthesis of the most significant heterocyclic compounds: furan, thiophene, pyrrole, pyridine, quinoline, indole. Properties and reactivity of the main p-deficient and p-excessive heteroaromatic compounds. Synthesis and properties of purines and pyrimidines. Hetero-organometallic compounds.
CONFORMATION AND STEREOCHEMISTRY. Fused cyclic systems. Unsaturated cyclic systems. Cycloalkanones. Condensed cyclic systems. Other cyclic systems.
METHODS OF FORMATION OF RINGS. Diels-Alder reaction, dienes and dienophiles. Features in disguise. Nef's reaction and the like. Lewis acids as catalysts. Diels-Alder reactions. Robinson ringing. Mannich base. Danishefsky's ring-closing reaction. Ringing with isoxazoles. Other ring closure reactions. Alkaline cleavage of beta dicarbonyl compounds. Krapcho reactions. Perkin ring closure and the like. Synthesis of cyclopentanones and cyclopentenones.
PREPARATION OF SMALL RINGS. Cyclopropane and derivatives. Use of carbene. Simmons-Smith reaction. Decomposition of diazoketones. Synthesis of diazocarbonyls and metal-catalyzed cyclopropanations. Corey's synthesis of cyclopropanes. Hints of synthesis of cyclobutanes.
DANGEROUS REACTIONS. Theory of pericyclic reactions. Molecular orbitals of conjugated polyenes. Cycloaddition reactions. Cycloadditions [2 + 2]. Cycloadditions [4 + 2]. Electrocyclic reactions and stereochemistry of these reactions. Sigmatropic transpositions. Classification of sigmatropic transpositions and mechanism of sigmatropic transpositions. Examples of Cope and Claisen transpositions in organic synthesis. Ring expansions with diazoalkanes.
CHEMISTRY OF ORGANOMETALS. Magnesium. Lithium. Copper. Zinc. Nickel, Palladium. The 18 electron rule. Interaction of hydrocarbon binders with transition metals. Metal-ligand bond. Catalytic cycles and coupling reactions (Suzuky, Negishi, Stille, Sonogashira etc.). The reaction of Heck and Tsuji-trost. Reactions of C-H activation.
ALKYLATIONS OF CARBON NUCLEOPHILES INTERMEDIATES. Generation of carbanions by deprotonation. Regioselectivity in the formation of the enolate. Alkylation of enolates. Generation and alkylation of dianions. Effects of the medium in the alkylation of enolates. C-alkylation and O-alkylation. Alkylation via enamines. Alkylation of enolates derived from the reduction of enones. Use of blocking groups. Use of activating groups. Michael's reaction. Alkylation of 1,3-dithian carbanions.
METHODS OF HYDRATION. Hydroboration-oxidation. Reduction of epoxides. Sulphonium ylides. Baeyer-Villiger reaction. Mitsunobu reaction.
METHODS OF DIHYDROXYLATION. Opening of epoxies. Use of Osmium tetroxide. Use of Potassium permanganate. Prevost's reaction. Woodward reaction. Corey-Das reaction. Cleavage of Criegee glycols. Lemieux-Rudloff reaction. Lemieux-Johnson reaction. Reaction of ozonolysis.
REDUCTIONS. Reductions with dissolved metals: Reduction of Birch. Reduction of unsaturated alpha-beta carbonyl compounds. Reduction of alkynes. Zinc-acid mixtures and Clemmensen reduction. Reductions with metal-hydrides. Felkin-Anh model. Wolff-Kischner reduction. Catalytic reduction. Reduction with diimide.
OXIDATION. Oxidation of primary alcohols to aldehydes. Pfitzner-Moffatt oxidation. Swern oxidation. Oxidation of secondary alcohols to ketones. Corey-Kim oxidation. Oxidation of allyl alcohols. Oxidation of allyl methylene groups (Riley oxidation).
HALOGENATION. Addition of HX to alkenes. Addition of X2 to alkenes. Halogenation of ketones. N-Bromoacetamide and N-bromosuccinimide. Transformations of functional groups to prepare organohalogens.
PREPARATION OF ALKENES. Elimination of Zaitsev. Hofmann Elimination. Beta-elimination reactions involving cyclic transition states: pyrolysis of N-oxides (Cope elimination). Elimination of selenoxides. Use of organo-titanium. Mc Murry's reaction, Tebbe. Metathesis of alkenes. Olefination of Julia and Julia-Kocienski. Wittig reaction. Modification by Schlosser. Horner-Woodsworth-Emmons reaction and Michaelis-Arbuzov reaction. Preparation of alkynes.
For the laboratory, various experiences will be carried out to acquire the basic manual skills and the various laboratory and bibliographic research techniques.