KNOWLEDGE AND UNDERSTANDING At the end of the course the student must have acquired advanced knowledge on modern methods of forming C-C and C-heteroatom bonds in organic synthesis. The objective of the course is to integrate the knowledge of organic chemistry obtained during the three-year degree course by providing a more synthetic and in-depth perspective, with particular reference to the preparation of multifunctionalized aromatic systems and the use of modern synthetic methods including organocatalysis and organophotocatalysis . Furthermore, particular aspects of commonly used methods will be explored in depth with the aim of elucidating their usefulness in particular conditions. APPLYING KNOWLEDGE AND UNDERSTANDING Students must be able to independently reason and plan organic syntheses of complex aromatic systems, also considering the new possibilities offered by non-conventional alternative methods. This must be done critically, with an in-depth analysis of the advantages and disadvantages related to the different synthetic steps. Students must be able to clearly understand the advantages relating to new methods and be able to compare them critically with the knowledge they already possess. MAKING JUDGEMENTS Independence of judgment is developed through preparation for the exam, which requires individual re-elaboration and assimilation of the theoretical material presented in the classroom and comparison with each student's previous knowledge. COMMUNICATION SKILLS The lessons will be carried out encouraging students to interact with the teacher. Given the master's level of the course, discussion with students will be encouraged in order to stimulate their critical spirit and communication skills. The ability to effectively communicate the knowledge acquired and one's ability to solve problems will be assessed during the exam by proposing synthetic problems and theoretical questions to which the student must be able to respond effectively. LEARNING SKILLS To stimulate the ability to learn knowledge, during the course exercises will be carried out in class and questions will be asked to students who will then propose solutions to be discussed in subsequent lessons. Furthermore, scientific manuscripts of interest will be submitted to students to discuss the reported synthetic methodologies. Students must be able to manage studying and learning autonomously.

in-depth knowledge of the organic chemistry topics required by the three-year degree in chemistry.

1) Methods for the synthesis and advanced functionalization of aromatic molecules. Synthetic design of polyfunctionalized aromatic systems and their preparation using organometallics and reactions for the formation of C-C and C-heteroatom bonds. Retrosynthetic approach for the preparation of aromatic and polyaromatic systems with particular attention to the importance of protecting groups in synthetic design. Examples of synthesis of complex aromatic systems of industrial and pharmaceutical interest. Synthesis and design of organic catalysts. 2) Synthesis and properties of polyaromatic, polyphenylene and nanographene systems. Importance of Clar's rules in the reactivity and properties of extended aromatic systems. Examples of important polyaromatic classes: acenes, perylenediimides, naphthalene diimides. Synthetic strategies for the synthesis of polyphenylene systems and their use in the synthesis of nanographenes. Bottom up methods of preparation of nanographenes based on organic synthesis. Advanced synthetic methods for heteroatom doping and its effect on the properties of materials, with reference to examples concerning the classes of extended aromatics discussed in the course. 3) unconventional synthetic methods in organic synthesis. Mechanochemistry, organic synthesis in flow and by microwaves and their uses. Advantages and problems compared to conventional synthesis in homogeneous solution. Examples of the use of these synthetic methodologies in the preparation of derivatives and molecules of interest. 4) Organocatalysis in organic synthesis Covalent Catalysis: types of catalysts, reactions and practical applications. Aminocatalysis. Non-covalent organocatalysis based on catalysts operating through hydrogen and halogen bonds. 5) Photocatalysis for organic synthesis: operating mechanisms of photocatalysis: single electron transfer, formation of donor/acceptor complexes, energy transfer. Homogeneous photocatalysis based on inorganic and organic catalysts. Heterogeneous photocatalysis and in flow systems.

“Organic chemistry” J. Clayden, N. Greeves, S. Warren, Oxford University Press and “visible light catalysis in organic chemistry” D. MacMillan, Wiley-VCH. Scientific publications suggested by teacher.

1a) Organometallic reagents and their reactivity discussed from the point of view of organic synthesis with particular focus on organolithiates, organozinc, and grignards and their use in the formation of Carbon-Carbon and Carbon-heteroatom bonds. Effect of aggregation on the reactivity of organolithiates and methods to increase their reactivity. 1b) Synthetic methods for the preparation of C-C and C-heteroatom bonds. Cross coupling and their practical use in the synthesis of complex aromatic substrates (Suzuki, Hiyama, Kumada, Stille, Negishi, Sonogashira, catalyzed iridium borylation). Ullmann coupling. Use of benzine and arynes in organic synthesis. Use of alkynes for the formation of C-C bonds. Formation of C-N bonds by Buchwald-Hartwig coupling, and C-N C-O bonds by Chan-Lam coupling. Synthesis of C-B bonds (boronic acids and esters) by coupling of miyaura, organolithiates and by reaction with bonds, C-Si, C-Ge, C-Sn). Synthesis of C-Si bonds and reactivity and properties of compounds containing organosilicon effect of silicon in alpha or beta. Synthesis of C-F and C-S bonds and their reactivity. Uncommon C-C bond formation methods (silicon ions, triazenes). Mallory and related photocyclization reactions for the formation of C-C bonds. 1c) Protection/deprotection of relevant functional groups in the chemistry of aromatic compounds: Carbonyls, carboxyls, alcohols, amines, thiols, alkynes. Evaluation of the usefulness of the different protective groups in the different situations required by complex syntheses. 2) Synthesis and applications of complex polyaromatic systems. Synthesis of polyphenylenes, cycloadditions based on tetraphenylcyclopentadienone and similar. Use of polyphenylenes as precursors of complex polyaromatic systems and nanographenes. Scholl reaction and dehydrogenation of polyphenylenes to form polyaromatic complexes and nanographenes. Synthetic methods for the preparation of functionalized polyaromatic derivatives and for the introduction of heteroatoms within aromatic systems. Clar's rules for the evaluation of the reactivity and aromaticity of polycyclic aromatic systems. Solubilizing groups for extended aromatic systems. 3) Solvent-free mechanochemical synthesis, types of reactors for mechanochemical reactions. Advantages and problems of the mechanochemical method in relation to the types of reactions previously discussed. Reactions carried out under mechanochemical conditions with organometallics. Mechanochemical Scholl reactions. Flow reactions, use of diazonium salts in flow to limit the risks associated with their use. Use of microwaves in organic chemistry: operating principles, choice of solvents and examples of reactions that benefit from the use of this synthetic methodology. 4) Organocatalysis in organic synthesis. Covalent Catalysis: types of catalysts, reactions and practical applications. Aminocatalysis. Examples of organocatalysts: The case of proline and Jorgensen catalysts. Non-covalent organocatalysis based on catalysts operating through hydrogen and halogen bonds. 5) Photocatalysis for organic synthesis: operating mechanisms of photocatalysis: single electron transfer, formation of donor/acceptor complexes, energy transfer. Homogeneous photocatalysis based on inorganic and organic catalysts. Importance of light sources and photocatalyst design. Heterogeneous photocatalysis and in flow systems. Practical examples of photocatalyzed reactions with particular reference to the use of organophotocatalysts.

Class lessons, teaching materials, exercises and questions that will be carried out in class and autonomously.

Any changes to the timetable or modifications due to exceptional situations will be communicated to students via moodle and institutional email.

The student's evaluation includes an oral exam in which an exercise is carried out followed by theory questions on the topics covered during the lessons. In particular, the exercise will consist of planning a synthesis of an organic molecule. The student must demonstrate that they are able to master the proposed topics both in their presentation and in using them to solve a practical problem. The score of the exam is attributed by means of a mark expressed out of thirty. To pass the exam (18/30) the student must demonstrate that he has acquired sufficient knowledge of the course topics, and be able to propose a theoretically correct solution to the exercise. To obtain the maximum score (30/30 with honors), the student must demonstrate that he/she has acquired an excellent knowledge of all the topics covered during the course but above all that he/she has a critical mindset in the use of theoretical tools, with the ability to weigh their strengths and weaknesses together with the ability to independently develop his/her own reasoning.

This course explores topics closely related to one or more goals of the United Nations 2030 Agenda for Sustainable Development (SDGs)