CATALYTIC METHODOLOGIES FOR FINE CHEMICALS

The teaching falls within the complementary training activities of the Master's degree program in Chemistry and Sustainable Technologies and allows the student to acquire the knowledge of important industrial catalytic processes for the production of fine chemicals.
The specific goal of the course is to provide knowledge of catalysis and its application in processes of industrial interest for the synthesis of fine chemicals, in particular of biologically active compounds such as drugs, agrochemicals, etc. Particular attention is due to the sustainability and use of solvents with a low environmental impact for the realization of biphasic catalytic processes. Therefore, the main objective will be the understanding of how catalytic methodologies can be used to plan new ways for the synthesis of fine chemicals by reducing the number of synthetic steps and thus decreasing the amount of waste.

1. Knowledge and understanding
i) To know the basic concepts of catalysis.
ii) To know the basics of industrial chemical processes.
2. Ability to apply knowledge and understanding
i) To know how to use the concepts learned to interpret a catalytic cycle.
ii) To know how to identify the characteristics to define an industrial process sustainable.
3. Ability to judge
i) To know how to evaluate the effectiveness of different synthetic ways of a process in terms of choice of catalysts, solvents and reaction conditions.
ii) To know how to evaluate any errors and / or causes that have led to unexpected results in the laboratory experiments.
4. Communication skills
i) To know how to communicate the knowledge learned and the result of their application using appropriate terminology, both in the oral and in written reports.
ii) To know how to interact with the teacher and with the classmates in a respectful and constructive way; in particular, to show availability and collaboration during group laboratory experiments.
5. Learning skills
i) Being able to take notes and to evaluate which are the most important information.

It is important to have achieved the training objectives of the Industrial Chemistry course and therefore to know what an industrial chemical process is. It is also necessary for the students to know the concepts of chirality and to possess a basic knowledge of catalysis. It is therefore recommended that the students have passed the Chemistry and Technology of Catalysis exam and followed the Industrial Chemistry II course.

In relation to the training objectives and expected learning outcomes, reported in the relative sections, the contents of the course can be divided as follows:
- Introduction.
Description of the program, methods of examination and bibliography.
- General aspects of catalysis.
The principles of Green Chemistry. Catalysts. Homogeneous and heterogeneous catalysis. Biphasic catalysis. Asymmetric catalysis. The importance of catalysis in industrial processes. Application of catalysis for the synthesis of fine chemicals.
- Catalytic hydrogenation reactions
The hydrogenation reaction. Homogeneous catalysts based on transition metals. Mechanism of the hydrogenation reaction: catalytic cycle.
- L-DOPA
Introduction. Preparation of the pharmaceutical ingredient L-DOPA (anti-Parkinson's) by means of resolution processes. Studies for the synthesis of L-DOPA by enantioselective hydrogenation. Search for a catalyst for enantioselective hydrogenation. Preparation of a new phosphine ligand for the hydrogenation reaction. The industrial process for the synthesis of the drug.
Studies for the synthesis of L-DOPA by enantioselective hydrogenation catalyzed by complexes of Rhodium modified with carbohydrates. Development of the industrial process. Comparison of the two industrial methods.
- Metolachlor
Introduction. Preparation of the racemic herbicide Metolachlor. Application of enantioselective hydrogenation for the synthesis of the enantiomerically enriched Metolachlor. Search for a new catalytic system based on Iridium. Development of a new enantiomerically pure diphosphine ligand. Study of the characteristics of the industrial process.
Metalaxyl and Clozylacon
Enantioselective catalytic hydrogenation for the synthesis of the two fungicides Metalaxyl and Clozylacon. Study of new enantioselective homogeneous catalytic systems.
Sharpless epoxidation
Introduction to the epoxidation reaction. Enantioselective epoxidation of Sharpless. Study of the catalytic system. Hypotheses on the structure of the catalyst and on the catalytic cycle. Applications of enantiomerically enriched epoxy alcohols obtained by Sharpless epoxidation.
Esomeprazole
Introduction. Action and preparation of Omeprazole, a pharmacologically active principle against stomach acidity. Preparation of Esomeprazole (enantiomerically enriched Omeprazole) by resolution methods. Study of an enantioselective catalytic system for the oxidation of sulphides to sulfoxides. Application of the new catalytic system for the preparation of Esomeprazole. The industrial process for the synthesis of the drug.
Alternative solvents and biphasic catalysis
Solvents in organic reactions. Solvents with a low environmental impact: water, perfluorinated solvents, ionic liquids, supercritical fluids. Biphasic catalysis using the aforementioned solvents. Strengths and weaknesses of biphasic catalysis. Application of biphasic catalysis.

1) H.U. Blaser, "Asymmetric Catalysis on an Industrial Scale", Wiley-VCH 2004.
2) B. Cornils, W.A. Herrmann, I.T. Horvath, W. Leitner, S. Mecking, H. Olivier-Bourbigou, D. Vogt (Eds.), Multiphase Homogeneous Catalysis, Wiley-VCH, Weinheim 2005.
3) Lecture notes.

The verification of learning takes place through an oral test. The students must demonstrate to know the topics related to the program of the course by answering some questions in a clear and correct way by using an appropriate language. The oral exam lasts from 30 minutes to 45 minutes depending on the clarity and consistency of the answers to the questions asked and at least three questions are provided.

Teaching is organized in lectures. The topics presented during the lessons are illustrated in detail using power point slides projected on a screen. The teaching material shown in the classroom can be downloaded from the University's "moodle" platform.

Italian

The course can be considered sustainable as it deals with catalysts and their application: catalysts allow to carry out chemical reactions with a lower environmental impact and lower energy costs, thus falling within the twelve principles of Green Chemistry. The use of solvents with a low environmental impact and the possibility of performing a biphasic catalysis with recovery and recycling of the catalyst allow a chemical process to be carried out in a more sustainable way.

Accessibility, Disability and Inclusion
Accomodations and Support Services for students with disabilities or specific learning disorders: Ca 'Foscari applies the Italian Law (Law 17/1999, Law 170/2010) for support services and accommodation available to students with disabilities or specific learning disorders. In case of motor, visual disability, hearing or other disabilities (Law 17/1999) or a specific learning disorder (Law 170/2010) and support is needed (assistance in the classroom, technological aids for exams) o individualized exams, material in accessible format, notes collection, specialized tutoring in support of the study, interpreters or other), contact the Disability office and DSA disabilita@unive.it.

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