| Educational guide Faculty of Chemistry |
english |
| Synthesis, Catalysis and Molecular Design (2013) |
 Subjects |
| ASYMMETRIC SYNTHESIS |
| Contents |
| IDENTIFYING DATA | 2020_21 |
| Subject | ASYMMETRIC SYNTHESIS | Code | 13685204 | |||||
| Study programme |
|
Cycle | 2nd | |||||
| Descriptors | Credits | Type | Year | Period | ||||
| 4.5 | Optional | AN |
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| Competences | Learning aims | Contents |
| Planning | Methodologies | Personalized attention |
| Assessment | Sources of information | Recommendations |
| 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 |
