ORGANIC CHEMISTRY LABORATORY AND 3 -MOD.1

The course MOD 1 is planned for the students enrolled at the first year of degree course of Sustainable Chemistry and Technologies (Master's Degree Program) and it precedes MOD 2. The contents of both MOD 1 and MOD 2 characterize the educational activities of Master Degree Program. The whole of the contents of MOD 1 and MOD 2 represents the full program for the final exam. Along MOD 1 the students will increase the ability to use the basic reaction processes of organic chemistry for synthetic purposes. The students, on the basis of recent literature, will be successively guided through more complex and well-structured synthetic chemical space.
Will be described:
- a lot of selected processes, focusing the interest on the chemical aspects concerning the formation of C-C and C-heteroatom bonds, deeply analyzing in the meantime the stereo-chemical aspect implications inside the transformation, with the aim of explaining the crucial role of the combination of the molecular symmetry properties of reagents during the reaction pathway, which define, in particular, the stereochemical outcome;
- a large variety of methodologies of organic synthesis, useful to conceive and create complex organic skeletons, such as the introduction, transformation and removal of numerous functional groups;
- useful strategies concerning the formation of C-C (saturated and/or unsaturated) bond by means of the use of synthons, also poly-functionalized, starting from those characterized by simple molecular complexity;
- the most important methodologies suitable for the connection of C-O and C-N bonds, useful also to assemble, in particular, both aromatic and non aromatic N-, O- substituted heterocyclic rings.

Generally, the reported examples concern the synthesis of biologically active compounds or their intermediates, commonly used in pharmacological context..

Laboratory - The aim is to be qualified to employ the reactions of organic chemistry for synthetic purposes.

It is expected that the contestants could reach a level of ability that makes their able to be endowed with:
- deep knowledge of organic chemistry;
- autonomy;
- comprehension (with self- confidence) of complex information;
- implementation without errors in new contexts, carrying out analysis and synthesis;
- acquisition of the ability to express by a reach lexicon;
- improvement of the abstraction capability.

The final evaluation will be based on:
1) Knowledge: capability to recall information, specific and general concepts, methods and processes, models, structures, classifications.
2) Comprehension: capability to accept ideas, concepts and logic reasoning.
3) Commitment: capability to use specific concepts and capability to use it in new situations.
4) Capability: ability to analyze, to think critically, to synthesize information.
5) Communication skill.

It is strongly suggested the deep knowledge of the topics of the preceding courses of both Organic Chemistry 1 and Organic Chemistry 2 concerning, in particular, fundamental topics such as acid-base theory, chemical equilibrium, conformational analysis, basic concept of stereochemistry, aromaticity, nomenclature of chemical compounds, synthesis, reactivity, structure, retro-synthesis of traditional class of compounds: alkanes, alkenes, alkynes, halo-alkanes, ethers, alcohols, thiols, amines, carbonyl compounds (aldheydes and ketones) and their derivatives with alcohols and amines, carboxylic acid and derivatives . Structure, property and reactivity of carbocyclic aromatic systems (benzene, naphthalene and derivatives).

On the basis of the established goal, the program of MOD 1 will be presented describing the topics as follows:
1. How to use the reactions of organic chemistry to build and transform molecule. Methods of organic synthesis.
Retro-synthetic analysis - Forward-analysis - Target Oriented Synthesis - Diversity Oriented Synthesis – Donor and acceptor Synthons - Umpolung – Concept of atom economy- Corey’s synthesis of leukotrienes – Introduction to the synthetic use of organolithium species - The arylsulfonyl group as highly versatile synthetic tool: Stereo selective Pauson-Khand reaction – 2-Phenylsulfonyl substituted cycloepta-1,3-diene: Symmetric epoxidation (Jacobsen), stereo and chemio selective introduction of C1 donor synthons- Biomimetic synthesis: problems concerning Epibatidine and Santalol; Johnson’s cyclization and cholesterol – Rice’s total synthesis of morphine -Combinatorial Chemistry- Prostaglandins : Corey (sequential method) and Noyori (stereo-convergent method) strategies- NMR in organic chemistry.

2. Description of the most important synthetic methods in C-C bond formation and their use in the construction of more complex carbon skeletons starting from simple synthons or less complex structures.
Condensation Reactions – Conjugated Additions - Alkylations e Cyanation – Electrophylic Cyclisations – Assembly of di-and three-functionalised (small or more complex) synthons.
Coupling and Cross Coupling Reactions (Negishi, Heck, Suzuki, Stille, Grigg, Buchwald ) Organo-Mg and organo-Cu reagents: structure, reactivity and examples of synthetic applications (ring opening reaction of aziridine and oxyranes, preparation of (natural or unnatural) aminoacids- Alkenylation – Carbenic Processes – Pericyclic Reactions - C1, C2, C3 units omologations. Stereoselective omologation (C1, C2) processes (indacrinone and physostigmine)- Asymmetric 1,2-addition to carbonyl: Noyori reagents (Li/Mg /Binol), Asymmetric addition of Et2Zn/chiral Aminoalcohols to benzaldehyde (chiral amplification). Synthesis of alfa-Tocopherol (Vit. E). Substitution reactions to carbonyl group: strategies to modulate the reactivity, dialkyllithium cuprates, Weinreb’s amides (ketons from carboxylic acids). Dessymetrisation of imides (meso) by means of stereoselective deprotonation. Hajos-Wieckert’s synthesis of steroid systems trough stereoselective intramolecular ring closing (stereoselective discrimination between enantiotopic carbonyl groups with chiral amplification effect). Reformatsky condensation. Glycidic esters by Darzen reaction. Alkylation of Enolates: reactivity, kinetic and thermodynamic considerations. Alkylation of decalone in angular position. Michael addition: several examples. Paterno-Buchi’s [2+2] photo-cycloaddition.

The didactic material (slides and printable version) such as more specific literatute will be provided by the teacher.
For basic knowledge:

- J. McMurry, Chimica Organica, Piccin
- K. Peter; c. Vollhardt, N. E. Schore, Chimica Organica, Zanichelli
- J. G. Smith, Chimica Organica, McGraw-Hill
- M. Loudon, Chimica Organica, Edises
- R. T. Morrison - R. N. Boyd, Chimica Organica, Zanichelli

Chemistry of Heterocyclic compounds:
- J. A. Joule, K Mills, Heterocyclic Chemistry, Wiley
- G.A. Pagani, A. Abbotto, Chimica Eterociclica, Piccin
- D. Sica, F. Zollo, Chimica dei Composti Eterociclici Farmacologicamente Attivi, Piccin

Bio-active and natural products:
- P. M. Dewick, Medicine natural Products: a Biosynthetic approach 3rd ed.; Wiley Ed.
italian version by Piccin Ed.

Introduction to NMR:
- M. Hesse, H. Meier, B. Zech, Metodi spettroscopici nella chimica organica, Edises
- A. Randazzo, Guida pratica alla interpretazione di spettri NMR, Loghia

Contestants have to debate, in about 50-60 minutes, the topic introduced through the course. In special case of a different need, an “ad personam” final exam can be agreed upon alternative way. Contestants have the possibility to undergo their final exam in English or French language alternatively to the Italian one. In addition, contestants have the opportunity to start their exam by discussing in detail a topic as they like. In any case the contestants will demonstrate, in the final exam, their knowledge on the topics of the full program presented during the course.

The final evaluation will be based on :
- Knowledge: capability to recall information, specific and general concepts, methods and processes, models, structures, classifications.
- Comprehension: capability to accept ideas, concepts and logic reasoning.
- Commitment: capability to use specific concepts and capability to use it in new situations.
- Capability: ability to analyze, to think critically, to synthesize information.
- Communication skill.

The course is organized in a series of lessons and practice in laboratory. In class will be proposed a series of exercises concerning synthesis, mechanism of reactions, stereochemistry and elucidation of NMR spectra of organic compounds..

Italian

The contents of both Mod 1 and Mod 2 of Organic Chemistry 3 and laboratory constitute the full programme of the only one final exam. Attendance at laboratory sessions is necessary.

Laboratory's activities: Functional group transformations. Preparation of polyfunctionalized molecules through multistep reaction sequences. Synthesis of chiral compounds.
In addition, near the glassmaker, the students will learn some processing techniques concerning simple laboratory glassware under the supervision of experts .

oral

This subject deals with topics related to the macro-area "Human capital, health, education" and contributes to the achievement of one or more goals of U. N. Agenda for Sustainable Development