Module Specifications.
Current Academic Year 2024 - 2025
All Module information is indicative, and this portal is an interim interface pending the full upgrade of Coursebuilder and subsequent integration to the new DCU Student Information System (DCU Key).
As such, this is a point in time view of data which will be refreshed periodically. Some fields/data may not yet be available pending the completion of the full Coursebuilder upgrade and integration project. We will post status updates as they become available. Thank you for your patience and understanding.
Date posted: September 2024
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Description This modules discusses physical chemistry in the context of organic reactions – what determines reactivity of intermediates, how can reaction outcomes be predicted? This provides insight into mechanisms of reactions, for example those of reactive intermediates (radicals, 1,3-dipoles, carbenes, arynes, ylides). Frontier molecular orbital theory is also introduced. Also considered is selectivity of reactions, in particular in the context of three-dimensional chemistry. The concepts of reagent and substrate controlled stereochemistry in asymmetric synthesis are outlined. | |||||||||||||||||||||||||||||||||||||||||||
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Learning Outcomes 1. Identify well-known reactive intermediates and their reactions 2. Explain the reactivity of intermediates, based on thermodynamic and kinetic principles 3. Predict the products and selectivity of reaction pathways 4. Design regio- and stereoselective syntheses | |||||||||||||||||||||||||||||||||||||||||||
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
Physical organic chemistry (1 week)Review of fundamental principles of chemical thermodynamics and kinetics. Transition state theory. Reaction rate expressions. General relationships between thermodynamic stability and reaction rates. Kinetic versus thermodynamic control. Curtin-Hammett principle. Kinetic isotope effects. Linear free-energy relationships.Reactive intermediates (4 weeks)Introduction to reactive intermediates. Radicals: production, stability, conformations, solvent effects, abstraction, addition reactions, rearrangements. Carbenes and nitrenes, preparation and their reactions, electronic structure, singlet vs. triplet. Arynes: generation, structure, reaction with nucleophiles, cycloadditions. Synthesis and reactions of phosphorous and sulfur ylides. Wittig reaction and modifications.1,3-Dipoles: generation, structures, cycloaddition reactions, stereospecificity of reactions, frontier molecular orbital (FMO) theory.Asymmetric synthesis (5 weeks)Introduction: 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 | |||||||||||||||||||||||||||||||||||||||||||