METODI FISICI IN CHIMICA ORGANICA - CHIMICA ORGANICA 2

Module CHIMICA ORGANICA 2

The course aims to provide a critical and scientific mentality and rational use of mnemonic abilities, favoring the ability to apply theoretical knowledge to problem-solving.

This means overcoming the limit of mere "mnemonic repetition" of concepts that, in doing so, would be aimed at simple learning. Critical and scientific mentality at the same time constitute a high-level objective; it requires a synthesis between mental operation and actual realization: the first is expressed in the design of an experiment, in the rational-intuitive control of the execution and calculation phases and the evaluation phase of the results; the second is expressed in the actual execution of the experiment, even at the virtual level.

Therefore, at the end of the course, the student must be able to:

D1 KNOWLEDGE AND UNDERSTANDING ABILITY

• Know in-depth the reactivity of new classes of organic compounds and the reaction mechanisms through which they react.

• Illustrate the criteria that allow to carry out processes with a pronounced chemical, position, and stereochemical selectivity.

D2 ABILITY TO APPLY KNOWLEDGE AND UNDERSTANDING

• Identify the nature of the synthetic process to which the organic molecules are subjected based on the described reaction conditions.

• Correctly describe the reaction mechanism for the related processes.

• Discuss the nature of the selective processes that these mechanisms involve.

D3 AUTONOMY OF JUDGMENT

• Choose the most suitable reagents to carry out the required synthetic process with the desired selectivity degree.

• Use the most efficient method available to perform the synthesis of even multi-functionalized structures.

D4 COMMUNICATION SKILLS

• Communicate, using appropriate technical-scientific terminology, with the teacher and experts in the subject of study.

• Competently discuss, even in the context of an oral examination, the synthetic techniques learned.

D5 LEARNING SKILLS

• Find and learn the information, new compared to those provided during the training activity, necessary to broaden the knowledge on topics more or less correlated with those covered by the course.

• Understand and process the contents of scientific publications containing the results of new research.

• Use the knowledge acquired to make it easier to understand topics related to organic chemistry delivered in other educational activities.

Acid-base properties of organic compounds, basic stereochemistry, properties and reactivity of functional groups in organic chemistry.

Knowledge of an appropriate study method; the following sites and readings are recommended:

• http://studenti.unimi.it/studentestrategico/metodo/index.htm
• http://helpmetodo.altervista.org/
• https://www.mondadorieducation.it/media/contenuti/statici/didattica/flipped/assets/pdf/04_lavoro_casa.pdf

MODULE 1. BIO-ORGANIC COMPOUNDS

19/29/30. CHEMISTRY OF AROMATIC HETEROCYCLES

Classification of aromatic heterocycles - Heteroaromaticity - Electrophilic substitution: general aspects - Electronic systems: pentatomic heterocycles containing only one heteroatom - Preparation: Paal-Knorr synthesis of furan, pyrrole and thiophene - Synthesis of pyrrole Knorr - Synthesis of Feist-Bernary del furan and pyrrole Hantzsch synthesis - Reactivity: Acid-base, electrophilic substitution, addition and cycloaddition, oxidation and reduction reactions - Electron systems: benzocondensed pentatomic heterocycles containing only one heteroatom - Preparation: Fischer synthesis of indole - Reactivity: Acid-base, electrophilic substitution, oxidation and reduction reactions - Electron poor systems: exatomic heterocycles containing only one heteroatom - Preparation: Hantzsch synthesis of pyridine - Reactivity: Acid-base reactions, Nitrogen reactions with electrophiles , Electrophilic replacement reactions , of nucleophilic substitution, of oxidation and reduction - Pyridine N-oxide and electrophilic substitution - Electron-poor systems: benzocondensed heterocyclic heterocycles containing only one neutral heteroatom - Preparation: Skraup synthesis of quinoline, Bischler-Napieralski synthesis of isoquinoline - Reactivity: Main reactions.

20. THE ORGANIC CHEMISTRY OF CARBOHYDRATES

Classification of carbohydrates - The notation D and L - Configuration of aldoses - Configuration of ketoses - Reactions of monosaccharides in basic solution - Oxidation-reduction reactions of monosaccharides - Chain elongation: Kiliani-Fischer synthesis - Chain shortening: degradation of Wohl - Stereochemistry of glucose: the Fischer demonstration - Monosaccharides form cyclic hemiacetals - Glucose is the most stable among aldohexose - Glycosides formation - The anomeric effect - Reducing and non-reducing sugars - Disaccharides - Polysaccharides - Some natural products derived from carbohydrates - carbohydrates on the cell surface - synthetic sweeteners.

21. AMINO ACIDS, PEPTIDES, AND PROTEINS

Amino acid nomenclature - Amino acid configuration - Acid-base properties of amino acids - The isoelectric point - Amino acid separation - Amino acid synthesis methods - Resolution of a racemic amino acid mixture - Peptide bonds and disulfide bonds - Some interesting peptides - Synthesis strategies peptide - Automated peptide synthesis - Introduction to protein structure - How to determine the primary structure of a polypeptide or protein.

MODULE 2. SPECIAL TOPICS

27. SYNTHETIC POLYMERS

There are two main classes of synthetic polymers - Introduction to polymers for chain growth - Radical polymerization - Teflon: an accidental discovery - Recycling codes - Cationic polymerization - Anionic polymerization - Polymerization with ring-opening - Stereochemistry of polymerization • catalysts of Ziegler-Natta - Polymerization of dienes - Copolymers - Nanocontainers - Introduction to polymers for staged growth - Classes of polymers for staged growth - Health concerns: bisphenol A and phthalates - Designing a polymer - Physical properties of polymers - Melamine poisoning - Polymer recycling - Biodegradable polymers

28/34/35. PERICYCLIC REACTIONS

The three types of pericyclic reactions: Electrocyclic reactions, of cycloaddition and sigmatropic transpositions - Molecular orbitals and orbital symmetry - Electrocyclic reactions - Cycloaddition reactions - Sigmatropic transpositions - Summary of selection rules for pericyclic reactions. A new sort of reaction – General description of the Diels-Alder reaction – The frontier orbital description of cycloadditions – Regioselectivity in Diels-Alder reactions – The Woodward-Hoffmann description of the Diels-Alder reaction – Trapping reactive intermediates by cycloadditions – Other thermal cycloadditions – Photochemical [2 + 2] cycloadditions – Thermal [2 + 2] cycloadditions – Making five-membered rings: 1,3-dipolar cycloadditions – Two very important synthetic reactions: cycloaddition of alkenes with osmium tetroxide and with ozone – Sigmatropic rearrangements – Orbital descriptions of [3,3]-sigmatropic rearrangements – The direction of [3,3]-sigmatropic rearrangements – [2,3]-Sigmatropic rearrangements – [1,5]-Sigmatropic hydrogen shifts – Electrocyclic reactions.

36. Participation, rearrangement, and fragmentation

Neighbouring groups can accelerate substitution reactions – Rearrangements occur when a participating group ends up bonded to a different atom – Carbocations readily rearrange – The pinacol rearrangement – The dienone-phenol rearrangement – The benzylic acid rearrangement – The Favorskii rearrangement – Migration to oxygen: the Baeyer–Villiger reaction – The Beckmann rearrangement – Polarization of C–C bonds helps fragmentation – Fragmentations are controlled by stereochemistry – Ring expansion by fragmentation – Controlling double bonds using fragmentation – The synthesis of nootkatone: fragmentation showcase.

38. Synthesis and reactions of carbenes

Diazomethane makes methyl esters from carboxylic acids – Photolysis of diazomethane produces a carbene – How do we know that carbenes exist? – Ways to make carbenes – Carbenes can be divided into two types – How do carbenes react? – Carbenes react with alkenes to give cyclopropanes – Insertion into C–H bonds – Rearrangement reactions – Nitrenes are the nitrogen analogues of carbenes – Alkene metathesis.

11/40. Organometallic chemistry

Reazioni di accoppiamento catalizzate da palladio – Metatesi degli alcheni – Grubbs, Schrock, Suzuki ed Heck ricevono il premio Nobel – Transition metals extend the range of organic reactions – The 18 electron rule – Bonding and reactions in transition metal complexes – Palladium is the most widely used metal in homogeneous catalysis – The Heck reaction couples together an organic halide or triflate and an alkene – Cross-coupling of organometallics and halides – Allylic electrophiles are activated by palladium(0) – Palladium-catalysed amination of aromatic rings – Alkenes coordinated to palladium(II) are attacked by nucleophiles – Palladium catalysis in the total synthesis of a natural alkaloid – An overview of some other transition metals.

MODULE 3. Stereoselectivity

31. Saturated heterocycles and stereoelectronics

Introduction – The anomeric effect. Related effects in other types of compounds – Making heterocycles: ring-closing reactions.

33. Diastereoselectivity

Looking back – Prochirality – Additions to carbonyl groups can be diastereoselective even without rings.

1. Organic Chemistry – P. Y. Bruice – 8ª Ed. Pearson.
2. Organic Chemistry – J. Clayden, N. Greeves, and S. Warren – 2nd Ed. Oxford University Press.