| Competences |
| Type A | Code | Competences Specific |
| Common | ||
| AC2 | CE2-Develop a thorough knowledge of the most advanced applications in synthesis and catalysis. | |
| AC3 | CE3-Correctly apply the most advanced methodologies in synthesis and catalysis. | |
| AC6 | CE6-Have a fluent command of the specialized terminology in English related to the fields of synthesis, catalysis and molecular design. | |
| AC8 | CE8-Design synthesis routes for new products using modern techniques of chemical synthesis, chemical and physical structural characterization, high performance experimentation, data analysis and computational chemistry. | |
| AC9 | CE9-Develop a thorough knowledge of the modern techniques for discovering and optimizing new synthetic processes and new catalysers. | |
| Type B | Code | Competences Transversal |
| Common | ||
| BC5 | CT5-Communicate complex ideas effectively to all sorts of audiences | |
| BC7 | Apply ethical principles and social responsibility as a citizen and a professional. | |
| Type C | Code | Competences Nuclear |
| Learning aims |
| Objectives | Competences | ||
| Understanding the advanced aspects of the stereochemistry of organic and organometallic compounds, tropism, prochirality, etc. | AC2 AC6 |
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| Understanding the methods of assymetric synthesis based on transition metals, organic catalysis, enzymatic catalysis, and the industrial procedures currently used in catalysis. | AC2 AC3 AC6 AC8 AC9 |
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| Applying the current techniques for determining enantiomeric excess, and understanding their advantages and limitations. | AC3 AC9 |
BC7 |
|
| Designing synthetic schemes that incorporate asymmetric synthesis processes. | AC8 |
BC5 |
|
| Contents |
| Topic | Sub-topic |
| 1. Fundamentals of Stereochemistry | Conformation. Configuration: Stereogenic units Chiral axes Chiral planes Helicity Topism and prochirality: substitution and addition criteria, simmetry criterion Topism and reactivity. Prochirality and Prostereoisomerism |
| 2. Strategies to enantiomerically enriched compounds. Determination of enantiomeric excess | Resolution by Crystallization: racemic compounds, pseudoracemates, conglomerates. Resolution by formation of diastereomers: resolving agents. Separation on enantiomers via inclusion compounds. Resolution by chromatography: Chiral Mobile Phases. Chiral Stationary Phases, Molecular Impriting. Kinetic Resolution Asymmetric Synthesis: Substrate-controlled synthesis, Auxiliary-controlled synthesis, Reagent-controlled synthesis, Catalyst-controlled synthesis |
| 3. Carbonyl addition | 1,2-Asymmetric Induction in carbonyl addition. Diastereoselective addition of hydride donors to cyclic ketones Catalytic Enantioselective Addition of R2Zn reagents. Chiral Lewis base and acid catalysis. Asymmetric amplification. Autocatalytic asymmetric alkylation. Asymmetric autocatalysis with enantiopurity amplification. Enantioselective Ketone Reduction: Chiral aluminun reagents: Binaphthyl Ligands (BINAL-H), Aminoalcohol ligands Application in synthesis. Chiral boron reagents: Isopinocampheylborane, Alpine-borane, Chloroisopinocampheylborane (DIP-Cl) and derivatives, borolanes (Masamune reagents). CBS-mediated reduction of ketones |
| 4. Functionalizations of enolates | auxiliaries: a) Chiral auxiliaries on acids and derivatives: Meyers’ Oxazolines. Prolinol amides. Pseudoephedrine amide. Oppolzer Sultams. Imides. Evans Oxazolidine. Other imides. Borneol and isoborneol esters derivatives. Bis-lactim esters. Creation of temporary stereogenic centres. “Self-reproduction” of chirality. b) Chiral auxiliaries on aldehydes and ketones: Imines and Hidrazones. Enantioselective enolate alkylations. Other reactions involving enolates. ?-Hydroxylation and amination to carbonyl group. |
| 5. Allylation of C=O bonds | Diastereoselective allylation of chiral aldehydes Enantioselective allylation of aldehydes with chiral reagents: Equivalence with aldol reaction. Types of reactions. Tartaric acid-derived boronatoes (Roush reagents). Brown’s dialkylboranes (isopinocampheylboranes). Other boranes. Titanium reagents Catalytic asymmetric allylations |
| 6. Aldol reaction | Substrate control with chiral carbonyl compounds Use of chiral auxiliaries Catalytic enantioselective aldol reactions: Acceptor activation: Mukaiyama reaction. Sn, Ti, Cu, B, Au, Ag catalysis. Donor activation: use of Lewis Bases: phosphoramides. Acceptor and donor activation: Bifunctional catalysts |
| 7. Conjugated addition reactions | Diastereoselective conjugated additions to optically active substrates Diastereoselective conjugated additions with chiral auxiliaries Catalytic conjugate additions |
| 8. Diels-Alder cycloaddition reaction | Diastereoselective Diels-Alder Reactions. Diastereoselective Diels-Alder reactions using chiral auxiliaries. Catalytic enantioselective Diels-Alder reactions |
| 9. Alkene hydroboration | Substrate-controlled diastereoselective hydroboration of acyclic alkenes. Asymmetric hydroboration with chiral boranes. Catalytic asymmetric hydroboration |
| 10. Metal-catalyzed allylations | Diastereoselective palladium-catalyzed allylation reactions. Enantioselective palladium -catalyzed allylation reactions. |
| 11. Asymmetric palladium-catalysed coupling reactions | |
| 12. Oxidation of alkenes | Epoxidations. Asymmetric Ring.Opening of epoxides. B) Dihydroxylation: Diastereoselective dihydroxylation of alkenes. Enantioselective dihydroxylation. |
| 13. Asymmetric Sigmatropic rearrangement | Diastereoselective Claisen rearrangement. Diastereoselective Claisen rearrangement using chiral auxiliaries. Enantioselective Claisen rearrangments. |
| 14. Asymmetric alkene metathesis | |
| 15. Organocatalysis | |
| 16. Enzymatic catalysis |
| Planning |
| Methodologies :: Tests | |||||||||
| Competences | (*) Class hours | Hours outside the classroom | (**) Total hours | ||||||
| Introductory activities |
|
0.5 | 0 | 0.5 | |||||
| Lecture |
|
25 | 37.5 | 62.5 | |||||
| Problem solving, exercises in the classroom |
|
14 | 28 | 42 | |||||
| Personal attention |
|
1 | 0 | 1 | |||||
| Short-answer objective tests |
|
3 | 4 | 7 | |||||
| (*) On e-learning, hours of virtual attendance of the teacher. (**) The information in the planning table is for guidance only and does not take into account the heterogeneity of the students. | |||||||||
| Methodologies |
| Description | |
| Introductory activities | Presentation of the subject. |
| Lecture | Presentation of subject contents. |
| Problem solving, exercises in the classroom | Extension and discussion of the lecture contents |
| Personal attention | Time that each teacher has to speak to pupils and resolve their doubts. |
| Personalized attention |
|
|
| Assessment |
| Description | Weight | ||
| Problem solving, exercises in the classroom | Throughout the course students will discuss in class the exercises previously handed out. | 40% | |
| Short-answer objective tests | Examen oral o escrit dels continguts de l'assignatura | 60% | |
| Others | Participació activa a classe |
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| Other comments and second exam session | |||
|
During the exams, any mobil telephone, tablet or other device that has not been expressly authorized for the exam must be switched off and out of view. Any attempt to pass any exam of any subject by fraudulent means (be this physical or electronic) will result in the student being awarded a fail for the exam in question. In addition to this, the gravity of the offence may lead the faculty/school to propose that the student be subjected to disciplinary proceedings, which will be initiated by a resolution from the rector. |
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| Sources of information |
| Basic |
Ager, D.J.; East, M.B. , Asymmetric Synthetic Methodology, CRC Press, 1996
Astruc, D. ed., Méthodes et techniques de la chimie organique, Presses Uiversitaires de Grenoble, 1999
Atkinson, R., Stereoselective synthesis, John-Wiley, 1995
Bäckvall, J.-E. , Modern Oxidation Methods, Wiley-VCH, 2004
Berkessel, A.; Gröger, H., Asymmetric Organocatalysis. From Biomimetic Concepts to Applications in Asymmetric Synthesis, Wiley-VCH, 2005
Boger, D.L., Modern Organic Synthesis, TSRI Press, 1999
Brückner, R., dvanced Organic Chemistry, A Hartcourt Academic Press, 2002
Carey, F. A.; Sundberg, R. J., Advanced Organic Chemistry, part A and B, Springer, 2007
Carreira, E.; Kvaerno, L., Classics in Stereoselective Synthesis, Wiley-VCH, 2009
Carruthers, W.; Coldham, I., Modern Methods of Organic Synthesis, Cambridge University Press, 4th Ed., 2004
Christmann, M.; Bräse, S., Asymmetric Synthesis. The Essentials, 2 nd edition, Wiley-VCH, 2008
Collins, A.N.; Sheldrake, G.N.; Crosby, J., Chirality in Industry, John Wiley, 1992
Collins, A.N.; Sheldrake, G.N.; Crosby. J. , Chirality in Industry, John Wiley , 1997
Crabtree, R. H., The Organometallic Chemistry of the Transition Metals, Wiley, 2005
Dalko, P.I., Enantioselective Organocatalysis. Reactions and Experimental Procedures, Wiley-VCH, 2007
Eliel; E.L.; Wilen, S.H., Stereochemistry of organic compounds, Wiley Interscience, 1994
Jacobsen, E.N.; Pfaltz, A.; Yamamoto. H., Comprehensive Asymmetric Catalysls I-III, Springer, 1999
Katsuki, T. , Asymmetric Oxidation Reactions, Oxford University Press, 2001
Lin, Q.G.; li, Y.M.; Chan, A.S.C., Principles and applications of asymmetric synthesis', Wiley, 2001
Mahrwald, R. , Modern Aldol Reactions 2 volumes, Wiley-VCH, 2004
Mikami, K.; Lautens, M. , New Frontiers in Asymmetric Catalysis, Wiley, 2007
Ojma, I. , Catalytic Asymmetric Synthesis, John Wiley, 2nd ed., 2000
Procter, G., Asymmetric synthesis, Oxford University press, 1996
Procter, G. , Stereoselectivity in Organic Synthesis, Oxford University press , 1998
Rizzacasa.M.A., Stoichiometric asymmetric synthesis, Sheffleld Academic Press, Blackwell Sclence, 2000
Seyden-Penne, J.; Curran, D.P., Chiral auxiliaries and ligands in asymmetric synthesis, John Wiley, 1995
Stephenson, G.R. ed., Advanced Asymmetric Synthesis, Blackie Academic and Professlonal, 1996
Walsh, P.; Kowzlowski, M., Fundamentals of Asymmetric Catalysis, University Science Books, 2009
Ward, R.S., Selectivity in Organic Synthesis, John Wiley , 1999 |
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| Complementary | |||||||||
| Recommendations |
(*)The teaching guide is the document in which the URV publishes the information about all its courses. It is a public document and cannot be modified. Only in exceptional cases can it be revised by the competent agent or duly revised so that it is in line with current legislation.