NEW FRONTIERS IN HOMOGENEOUS CATALYSIS

The course New Frontiers in Homogeneous Catalysis, despite being among the similar / integrative courses, in the previous years has met an increasing interest from the students because it is focused on innovative aspects related to homogeneous catalysis which is one of the cornerstones of chemical synthesis and of new production technologies. The course is in fact perfectly framed within the degree Chemistry and Sustainable Technologies considering that the issues addressed concern all the new approaches to homogeneous catalysis that arise in academic research and which are becoming reality in industrial production before small and then on a medium scale. These issues are all aimed at greater energy sustainability, the improvement of the impact on human health, the environment and all aspects of safety that are the cornerstones of the course of studies in Chemistry and Sustainable Technologies.

The expected learning outcomes can be divided into the following specific aspects:
1. Knowledge and understanding i) know the different approaches to the innovative homogeneous catalysis that are part of the course topics, ii) demonstrate to have learned the intrinsic limits of application, the advantages and disadvantages of each one
2. Ability to apply knowledge and understanding i) know how to relate the topics of the course to each other, gathering points of contact, similarities and specificities, ii) to know and to have learned the similarities between the innovative catalytic methods in homogeneous catalysis and the basic action of the enzymes.
3. Ability to judge i) know how to choose between the different innovative catalytic methods the one that best fits a hypothetical case of catalytic reaction to be developed on the basis of elements such as experimental conditions, type of solvent, selectivity, catalytic activity, ii) know how to propose effective recycling methods of the catalytic system aiming at the sustainability of the process.
4. Communicative skills. Know how to communicate constructively with the teacher both in oral form and reporting writing on a sheet, using the correct terminology and nomenclature, in a way that is as synthetic as possible, with sufficient confidence.
5. Learning skills. Know how to integrate the didactic material provided by the teacher with personal clear notes to be related to the rest of the teaching material. Knowing how to grasp the key passages of the lessons in the form of personal notes to be able to relate the different topics of the course and to understand the basic aspects of the course.

Considering the interdisciplinarity of the present course, among the prerequisites there have been achieved the training objectives of the three-year degree courses in Chemistry, in particular of Organic Chemistry 1 and 2 courses as it is required that the student is familiar with the reactivity of the groups functional and with the concepts of symmetry and selectivity, of General Chemistry as it requires knowledge related to the structure and reactivity of Lewis acids and organometallic complexes and the basis of some catalytic cycles.

Introduction
Introduction to the course, exam methods and teaching material. Importance of catalysis in chemical synthesis, impact of catalysis on society, examples of Nobel prizes related to homogeneous catalysis, recapitulation of the basic functioning of enzymes. Review of the concept of selectivity, from chemoselectivity to enantioselectivity and relation with the energy profile of chemical reactions.
Mechanochemistry
Description of mechanochemistry, reactions in the absence of solvent, chemical and physical aspects of the use of mechanical energy in chemical synthesis, operation of the ball mill, examples in the synthesis of metal alloys, examples in the formulation of co-crystals. Flow Vortex System, application in organic synthesis and inorganic materials preparation.
Sonochemistry
Use of ultrasound in chemical synthesis, physical aspects of the propagation of acoustic waves in solids and liquids, cavitation, application in multi-phase solid-liquid reaction. Application examples in cross-coupling reactions, organic synthesis reactions, examples of chemo and product regioselectivity.
Microwave reactions
Physical aspects of microwaves and interaction with matter, choice of solvent in microwave reactions, relationship between reaction T and solvent properties, examples in organic synthesis with focus on selectivity and efficiency of reactions, examples of multicomponent reactions, examples in reactions catalyzed by metals or organocatalysts, examples in total synthesis.
Multi-phase catalysis for the recycling of the catalyst
Liquid-liquid systems with historical background on ethylene trimerization and Rhone Poulenc hydroformylation, use of ionic liquids, fluoridated liquids, supercritical CO2, interaction between CO2 and solvents, reversible solvents, catalysts on reversible polymers, reversible catalysts by chemical and physical stimulation (light)
Heterogenization of homogeneous catalysts
Comparison of homogeneous and heterogeneous catalysis, covalent modification of the binder, length of the binder spacer, ionic modification and heterogenization by weak interactions, ionic pair and hydrogen bond, "ship in the bottle" heterogenization approach. Choice of heterogeneous supports, effects of support on enantio and diastereoselectivity, recyclable magnetic catalysts.
Homogeneous catalysts of Fe
History of Fe in homogeneous catalysis, relationship between type of reactions, oxidation state of Fe and nature of the ligand (hard/soft), examples of selective reactions of hydrogenation, oxidation, formation of C-C bonds, C-heteroatom, polymerizations.
Organocatalysis
Covalent organocatalysis, proline catalysis, imino-enamine cycle, relation between catalyst and product stereochemistry, carbonyl reaction with electrophiles in alpha position, oxidation with chiral ketones via dioxirane, activation of Lewis RSiCl3 acids with chiral Lewis bases, hydrogen bond interactions or ionic pair between catalyst organ and substrate, chiral phase transfer catalysis , catalysis from chiral cavities such as cyclodextrins, hints of catalysis with polymers templated by analogues of transition states.
Micellar catalysis
Hydrophobic (entropic) effect at the base of micelle formation, similitude with enzymes, description of surfactants, micellar catalysis in condensation reactions, micellar catalysis combined with metal catalysis, concentration effect and micellar anisotropy, examples in reaction formation of C-C bonds , micelle-mediated substrate selectivity.
Supramolecular catalysis
Application in equilibrium reactions, application in irreversible reactions and product inhibition, application in reactions in which they lead to acceleration as well as turnover. Examples of substrate selectivity with supramolecular capsules.

Asymmetric Organocatalysis - From Biomimetic Concepts to Applications in Asymmetric Synthesis
A. Berkessel and H. Groger
John Wiley & Sons, 2005

Iron Catalysis in Organic Chemistry: Reactions and Applications
Bernd Plietker
John Wiley & Sons, 2008

Supramolecular Catalysis
Piet W.N.M. van Leeuwen
John Wiley & Sons, 2008
Slides of the lessons available on the Moodle platform

Oral exam during which the student will be asked to report in writing examples of reactions, catalytic methods, chemical transformations and catalytic cycles. During the exam the teacher will asked questions of descriptive character to which the student will have to answer demonstrating to know the topics of the course. Other questions will be asked to ensure that the student has deeply understood the logic, the fields of application, the limits and complementarities (see expected learning outcomes).

The course is organized into two hours lectures during which the topics of the course are presented. In order to stimulate the attention of the students the teacher periodically organizes before the end of the lesson a series of short tests (5-10 min) that students will follow directly anonymously on their electronic devices (smartphone, tablet, etc.) exploiting the potential of the Socrative platform (https://www.socrative.com/ ). In this way the teacher will be able to monitor the learning progress during the lessons in order to be able to take up in the next lessons some concepts that may be less easily understood by the students.
On the University's "moodle" platform there are pdf files related to slides of the presentations projected during the lessons. Moreover, from the Socrative platform, students will still be able to keep track of their tests (not relevant for the final exam as anonymous) and will be encouraged to interact with the teacher in order to ensure their maximum understanding of the course.

Italian

The teacher is available for discussion with the students on the topics of the course, Please, get in contact by email: alesca@unive.it
Accessibility, Disability and Inclusion
Accommodation and support services for students with disabilities and students with specific learning impairments:
Ca’ Foscari abides by Italian Law (Law 17/1999; Law 170/2010) regarding support
services and accommodation available to students with disabilities. This includes students with mobility, visual, hearing and other disabilities (Law 17/1999), and specific learning impairments (Law 170/2010). In the case of disability or impairment that requires accommodations (i.e., alternate testing, readers, note takers or interpreters) please contact the Disability and Accessibility Offices in Student Services: disabilita@unive.it

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