Registry
Module Specifications
Archived Version 2013 - 2014
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Description To impart to the student the importance of three-dimensional thought in Chemistry. The module will concentrate on reactive intermediates with emphasis on their generation, detection and synthetic utility. The concept of reagent and substrate controlled stereochemistry in asymmetric synthesis will be introduced to the students. | |||||||||||||||||||||||||||||||||||||||||
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Learning Outcomes 1. Demonstrate the concept of reactivity with respect to intermediates 2. Identify well-known reactive intermediates 3. Appreciate the utility of reactive intermediates. 4. Show the role of the concept of selectivity in reaction pathways 5. Demonstrate the reactions that the classes of compound listed under Indicative Syllabus 6. Apply concept of 3D structure to reactions under indicative syllabus 7. Ability to design regio- and stereoselective syntheses 8. Demonstrate knowledge of reactions used to form C-C bonds. | |||||||||||||||||||||||||||||||||||||||||
All module information is indicative and subject to change. For further information,students are advised to refer to the University's Marks and Standards and Programme Specific Regulations at: http://www.dcu.ie/registry/examinations/index.shtml |
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Indicative Content and
Learning Activities REACTIVE INTERMEDIATESIntroduction to reactive intermediates. Free radicals: production, stability, conformations, solvent effects, abstraction, addition reactions, rearrangements. Radicals in synthesis: alkane halogenations, radical oxidations. Carbenes and nitrenes, preparation and their reactions, electronic structure, singlet vs. triplet.Arynes: generation, structure, reaction with nucleophiles, cycloadditions.Carbenes: generation, structures, triplet vs. singlet carbenes, reactions1,3-Dipoles: generation, structures, cycloaddition reactions, stereospecificity of reactions. Synthesis and reactions of phosphorous and sulfur ylides. Wittig reaction and modifications.2. Molecular re-arrangements: C to C migrations. Migratory aptitudes, anchimeric assistance and neighbouring group participation. Pinacol and related rearrangements3. Aromatic heterocyclic chemistry: pi-excessive and pi deficient rings, synthesis of heterocyclic compounds, (pyridine, pyrene, furan, thiophone, indole, quinoline, isoquinoline). Reactions of heterocycles with nucleophiles and electrophiles.Asymmetric SynthesisIntroduction: What is asymmetric synthesis? How to control selectivity?Part A: C-C bond formation.Nucleophilic addition to carbonyl compounds: Substrate control and Reagent control. Cram's model, Felkin-Anh model, Stereoselectivity of enolate formation. Alkylation of enolates. The aldol reaction. Chiral Auxiliaries. Asymmetric Aldol reaction. Nucleophilic addition to imine compounds. Mannich Reaction. Asymmetric Friedel Crafts.Part B: Asymmetric reduction. Organoboranes, hydrogenation (substrate control) Part C: Asymmetric addition to C=C. Hydroboration, Hydrosilyation, Epoxidation, Aziridination, Dihydroxylation, Hydroamination. | |||||||||||||||||||||||||||||||||||||||||
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Indicative Reading List | |||||||||||||||||||||||||||||||||||||||||
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Other Resources None | |||||||||||||||||||||||||||||||||||||||||
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