Learning objectives
At the end of the course the student is expected to be able to:
- understand and use a correct stereochemical language concerning organic compounds
- have the knowledge necessary to understand stereoselective, stereospecific reactions and asymmetric induction
- be able to choose the most suitable methods for determining the enantiomeric composition of a chiral compound
- know the main chiro-optical techniques.
- discuss different types of organic reactions presented during the course, with a focus on the stereochemical outcome
- know different approaches for the functionalization of solid materials, both surfaces and nanomaterials as nanoparticles.
- know the fundamental concepts of 'green chemistry'
Prerequisites
- - -
Course unit content
Role of chirality in nature. Organic stereochemistry: review of the molecular chirality concepts due to center, axis, plane of chirality, helicity. Atropoisomerism and biphenyls. Study of dynamic phenomena by NMR spectroscopy. Time scale in NMR, IR and UV spectroscopies. Conformational analysis by NMR: thermodynamic and kinetic aspects Chirooptical methods: polarimetry; circular dichroism (CD) and its application in configurational and conformational studies (octant rule).
Determination of the enantiomeric composition by chromatographic and NMR methods. Conglomerates. Resolution of racemates, with examples of large scale applications.
Stereoselective and stereospecific reactions. 1,2-Concerted rearrangements involving C, O and N atoms, including stereochemical outcome. Diastereo- and enantioselective syntheses. Stereochemical outcome in aldolic condensations under thermodynamic or kinetic control. Pericyclic reactions. Diels-Alder reactions, electrocyclic and sigmatropic reactions.
Epoxidation reactions (with electrophilic or nucleophiles. Enantioselective epoxidation using Sharpless as well as Jacobsen-Katsuki chiral catalysts. Chirality amplification. Origin of chirality in nature. Chirality and biological effects. Additional organic reactions (e.g. click chemistry). Heterogeneous catalysts for organic synthesis. Supported catalysts. Functionalisation of solid supports with (chiral) metal complexes and biomolecules for enantioselective processes. Functionalization of nanomaterials.
The twelve principles of the Green Chemistry. Sustainable development and eco-compatibility of chemical processes. New reaction media: water, supercritical fluids, ionic liquids. Examples of environmental friendly industrial processes and comparison with traditional ones.
Introduction to the structure-reactivity relationship: Hammett equation, rho and sigma parameters.
Full programme
Role of chirality in nature. Organic stereochemistry: review of the molecular chirality concepts due to center, axis, plane of chirality, elicity as well atropoisomerism. Chirooptical methods: polarimetry; circular dicroism (CD) and its application in conformational and configurational studies (octant rule). Study of dynamic phenomena by NMR spectroscopy. Time scale in NMR, IR and UV spectroscopies. Conformational analysis by NMR: thermodynamic and kinetic aspects.
Determination of the enantiomeric composition by chromatographic and NMR methods. Stereoselective and stereospecific reactions. 1,2-Concerted rearrangements involving C, O and N atoms. Diastereo- and enantioselective syntheses. Aldolic condensations and Diels-Alder reactions. Pericyclic reactions. Epoxidation reactions and use of Sharpless as well as Jacobsen-Katsuki chiral catalysts. Chirality amplification. Origin of chirality in nature. Chirality and biological effects. Additional organic reactions (e.g. click chemistry). Heterogeneous catalysts for enantioselective reactions. Supported catalysts. Functionalisation of solid supports with (chiral) metal complexes and biomolecules for enantioselective processes. Functionalization of (nano)materials.
Sustainable development and eco-compatibility of chemical processes. The twelve principles of the Green Chemistry. New reaction media: water, supercritical fluids, ionic liquids. Heterogeneous catalysis. Examples of environmental friendly industrial processes and comparison with traditional ones. Introduction to the stucture-reactivity relationship.
Bibliography
- F. A. Carey, R. A. Sundberg “Advanced Organic Chemistry” Springer;
- E.L. Eliel, S.H. Wilen “Stereochemistry of Organic Compounds” J.Wiley & Sons;
- R.A. Sheldon,I.Arends, U. Hanefeld- “Green Chemistry and Catalysis”, Wiley-VCH; - D.E. De Vos , I.F.J. Vankelecom, P.A. Jacobs - “Chiral Catalyst Immobilization and Recycling”, Wiley-VCH
- - E. V. Anslyn, D. A. Dougherty, "Modern Physical Organic Chemistry", University Science Book, Sausalito, California
• Literature references on various topics will be given to allow deeper study.
Teaching methods
Lessons.
The slides used during the lessons are available to students on the Elly platform and will be loaded on a monthly basis. The subscription to the online course is required to download the files containing the slides. In addition, references of original papers are furnished to permit a deeper study.
Assessment methods and criteria
The oral examination consists of a discussion of the topics dealt with during the course.
In particular, the acquisition of a correct stereochemical language will be verified, as well as the understanding the reaction mechanisms leading to stereoselective and enantioselective processes. Knowledge of concerted reactions and of various approaches to functionalise solid (nano) materials will be checked. Green chemistry approaches to synthesis will be discussed.
The oral test is evaluated on a scale of 0-30. The oral test shall be communicated immediately upon completion of the test;
Please note that online registration on the application is compulsory.
Other information
The teacher is available to the student for any clarifications or
explanations of the topics covered during the course.
