The educational objective of the course is the students' understanding of the structural characteristics, of the nomenclature, of the chemical-physical properties and of the reactivity of the main classes of organic compounds through the study of the main reaction mechanisms.The course setting follows the classical criterion of the systematic description of the various functional groups, in both structural and reactionary terms. Some general topics such as the kinetic and thermodynamic aspects, acidity and basicity, stereochemistry, the relationships between structure and physical properties, will be treated separately. Other ones such as resonance, equilibria, electronic and steric factors, etc. are inserted into the discussion of functional groups in order to stimulate understanding and memorization by analyzing concrete examples.

Nucleophilic substitution at saturated carbon

Mechanism of first-order (SN1) and second-order (SN2) nucleophilic substitution, contrasts between SN1 and SN2, the leaving group in SN1 and SN2 reactions, the nucleophile in SN1 reactions, the nucleophile in SN2 reactions, nucleophiles and leaving groups compared , elimination and rearrangement reactions.

Elimination reactions

Substitution and elimination, how the nucleophile influences elimination versus substitution, E1 and E2 mechanisms. Substrate structure can enable E1, leaving group rule, Stereoselectivity in E1 reactions, periplanar transition state in E2, regioselectivity in E2, Stabilized Anions and alternative E1cB mechanism.

Review of spectroscopic methods

Spectroscopy and chemistry of the carbonyl group, IR spectroscopy of carboxylic acid derivatives, spectroscopic analysis of strained cyclic rings and alkynes, predicting the carbonyl stretching frequency, conformational analysis of cyclohexane via NMR spectroscopy, Couplings between heteronuclei, spectroscopic identification of products.

Electrophilic addition to alkenes

Addition of bromine, oxidation of alkenes to epoxides, regioselectivity to asymmetric alkenes, electrophilic addition to dienes, regioselective reactions of opening of asymmetric bromonium ions, stereospecific electrophilic additions, dihydroxylation, completely breaking the carbon-carbon double bond: scission with periodate and ozonolysis. Addition of water to the double bond.

Preparation and reactivity of enols and enolates.

Tautomerism: formation of enols by proton transfer, keto-enol equilibrium for aldehydes and ketones, experimental evidence of keto-enol equilibrium, acid and base catalyzed enolization, stable enols, consequences of enolization, reactions involving enols and enolates such as intermediates, stable equivalents of enolate anions, reactions of enols and enolates with oxygen: preparation of enol ethers and their reactions.

Electrophilic aromatic substitutions

Enols and phenols, electophilic substitution, activating/deactivating effects of the substituents present on the aromatic ring, orienting effects of the substituents present on the aromatic ring, reactions on polysubstituted aromatic compounds, peculiarities of electrophilic aromatic substitution reactions: advantages and disadvantages. Friedel Craft's reactions. Exploit the chemistry of the nitro group.

Conjugate additions and aromatic nucleophilic substitutions

Alkenes conjugated with carbonyl groups: electrophilic behavior of the alkene and carbonyl: conjugate additions and direct additions. Factors driving regioselectivity. conjugate substitution reactions, nucleophilic epoxidation, aromatic nucleophilic substitution, the addition-elimination mechanism: Nucleophilic substitution reactions via SN1: Diazonium salts. The mechanism via petrol.

Chemoselectivity and protecting groups

What is meant by selectivity, reducing agents, reduction of carbonyl groups, catalytic hydrogenation, removal of functional groups, reduction by dissolution of metals, selectivity in oxidation reactions, Competitive reactivity: which group reacts? Protective groups.

Regioselectivity

regioselectivity in aromatic electrophilic substitutions, electrophilic attack on alkenes, regioselectivity in radical reactions, nucleophilic attack on allyl compounds, electrophilic attack on conjugated dienes, conjugate additions, examples of regioselective reactions.

Alkylation of enolates

Different reactivities of carbonyl derivatives, Alkylation of nitriles and nitroalkanes, choice of electophile for alkylation, lithium enolates of carbonyl compounds and their alkylation, specific synthetic equivalents for the alkylation of aldehydes and ketones, alkylation of beta dicarbonyl compounds, regioselectivity of the alkylation of ketones, Michael acceptors.

Aldol condensation and Claisen condensation

The aldol reaction, equivalent nucleophiles of enols, control of aldol reactions of esters, aldehydes and ketones. intramolecular aldol reactions, carbon acylations, crossed ester condensations, synthesis of ketoesters by Claisen reaction, intramolecular crossed Claisen reactions.

Sulphur, silicon and phosphorus in organic chemistry.

Anions stabilized by sulfur, sulfonium salts, sulfonium ylides, comparison between silicon and carbon, nucleophilicity of allylic silanes, selective synthesis of alkenes. Selective synthesis of alkenes, alkene properties-geometry relationship, alkene equilibria, stereoselective synthesis of alkenes starting from alkynes, E alkenes via stereoselective reactions to alkynes. Julia olefination, Wittig reaction.

Retrosynthetic analysis

Disconnections attributable to known reactions, the synthons, multistep synthesis: control of chemoselectivity, functional group interconversion, C-C disconnections: starting materials, donor and acceptor synthons, functional groups with a 1.5 relationship, natural reactivity and umpolung.

Aromatic heterocycles: reactions

Heteroatomic aromatic compounds, pyridine, oxygen-containing six-membered aromaticin heterocycles, pentatomic heterocycles as substrates for electrophilic substitutions: furan, pyrrole and thiophene. Five- and six-membered rings with two nitrogen atoms. benzo-fused heterocycles, quinoline, and isoquinoline. Nitrogenous heterocycles containing sulfur and oxygen.

Aromatic heterocycles: synthesis

Synthesis of heterocycles: thermodynamic considerations, synthesis of pyrroles, thiophenes and furans from 1,4-dicarbonyl compounds. Hantzsch synthesis. Synthesis of pyrazoles and pyridazines from hydrazine and dicarbonyl compounds. Synthesis of pyrimidines and isoxazoles. Cycloadditions for the synthesis of tetrazoles and triazoles. Fischer synthesis of indoles. Synthesis of quinoline isoquinolines. the three main approaches for the synthesis of aromatic heterocycles.

 Organic chemistry and physical chemistry,  General and inorganic chemistry.

D1- KNOWLEDGE AND UNDERSTANDING The student must demonstrate the knowledge of the organic reactions associated with the main functional groups that distinguish the organic substances. Moreover he will have to demonstrate to be able to design synthetic sequences that involve more reactions that allow to elaborate processes of formation of complex molecules. These skills will be assessed through the resolution of a multi-step synthesis.

D2-APPLYING KNOWLEDGE AND UNDERSTANDING The student will have to show to apply his / her own knowledge, comprehension skills and ability to solve problems related to the behavior of organic substances inserted in a general context. These skills will be verified both  through specific oral applications.

D3-AUTONOMY OF JUDGMENT The student must have acquired knowledge such as to allow him to recognize and predict the behavior of complex molecules according to the reaction conditions to which they are subjected.

D4-COMMUNICATION The student must demonstrate that he / she is able to clearly communicate his / her conclusions, as well as the underlying knowledge and rationale, with an adequate chemical language, to specialist and non-specialist interlocutors. These skills will be verified through an oral test.

D5-LIFELONG LEARNING SKILLS The student must develop the ability to drive his path of scientific growth in a critical and autonomous way, being able to correctly use the study material provided by the teacher and the in-depth material that he himself can obtain. These abilities, as far as possible, will be stimulated by the teacher proposing in-depth studies and providing exercises to be solved at home during the course, which will then be explained and discussed during the lessons or hours of support activities.

The teaching material prepared by the lecturer in addition to recommended textbooks (such as for instance slides, lecture notes, exercises, bibliography) and communications from the lecturer specific to the course can be found inside the Moodle platform › blended.uniurb.it

All the lesson slides are available on Blended.

Teaching

Frontal lessons and exercises 

Innovative teaching methods

Problem-Based Learning

Attendance

Constant attendance at lessons is strongly recommended.

Course books

Jonathan Clayden, Nick Greeves, Stuart Warren, Organic chemistry, Oxford University Press

Assessment

The assessment of the student's preparation takes place through an oral test aimed at verifying the knowledge of the reaction mechanisms and the ability to interconnect the topics covered during the course. The average duration of the test is one hour.

Disability and Specific Learning Disorders (SLD)

Students who have registered their disability certification or SLD certification with the Inclusion and Right to Study Office can request to use conceptual maps (for keywords) during exams.

To this end, it is necessary to send the maps, two weeks before the exam date, to the course instructor, who will verify their compliance with the university guidelines and may request modifications.

Teaching

All the teaching material is available on the Blended platform for students who decide not to attend the course

Attendance

Constant attendance at lessons is strongly recommended.

Course books

To give students and non-attending students the opportunity to compensate for what is done during lessons with independent study, the following materials referring to the same contents of the program are indicated in order to promote full understanding:

Jonathan Clayden, Nick Greeves, Stuart Warren, Organic chemistry, Oxford University Press

Assessment

The exam is carried out on the blackboard and consists in the preliminary resolution of a multi-step summary taken from the scientific literature followed by a discussion on various topics covered during the course.

Disability and Specific Learning Disorders (SLD)

Students who have registered their disability certification or SLD certification with the Inclusion and Right to Study Office can request to use conceptual maps (for keywords) during exams.

To this end, it is necessary to send the maps, two weeks before the exam date, to the course instructor, who will verify their compliance with the university guidelines and may request modifications.