Module overview
Linked modules
Pre-requisite(s): CHEM3038 or CHEM6095
Aims and Objectives
Learning Outcomes
Learning Outcomes
Having successfully completed this module you will be able to:
- Describe the concept of chiral auxiliaries and their application in diastereoselective alkylation reactions. They should be able to explain the origins of the observed diastereoselectivity.
- Recognise situations where reactions may have different stereochemical outcomes, and be able to explain and/or predict the selectivity using appropriate stereoselectivity models.
- Use FMO theory to show that some pericyclic rections are allowed, others not, and that some have to take place with specific stereochemical consequences.
- Describe different approaches to the formation of carbanions, discuss their structures, stabilities/reactivities and applications in synthesis.
- Apply their detailed knowledge of radical chain reactions to rationalise the outcome of previously unseen examples of this genre.
- Describe the importance of kinetics and bond strength on the outcome of a radical chain reaction.
- Student should be able to plan syntheses using carbanions as nucleophiles or as precursors in palladium-catalysed C—C bond-forming reactions.
- Appreciate the likely course of a radical addition reaction when myriad options are, in principle, available (e.g. in casdade radical reactions).
- Illustrate how sulfones, phosphonium ylides and phosphonate can be used in synthesis for stereoselective olefination, and rationalise selectivity outcomes using stereoselectivity models.
- Appreciate when a radical addition reaction is likely or unlikely based on nature of the radical intermediate and the radical acceptor.
- Delineate the mechanistic and stereochemical course of some sophisticated cascade radical reactions and appreciate their value in target oriented synthesis.
- Describe the mechanistic course of various palladium catalysed coupling reactions (including Heck, Sonogashira, Negishi, Kumada Corriu, Stille, Suzuki etc.) and appreciate their value in synthesis.
- Appreciate problems associated with the use of organotin reagents and some of the ‘get rounds’ available.
- Describe stereoselectivity models for a variety of reactions including additions carbonyl compounds and enolate formation, and apply fundamental concepts such as conformational, steric and stereo electronic effects in rationalising stereochemical outcomes.
- Appreciate the class of pericyclic reactions and be able to identify them and draw mechanisms.
- Understand how the energy levels and orbital coefficients of components affect the rates and regiochemistry of cycloaddition reactions.
- Describe different organometallic reagents. They should be able to discuss their relative reactivities, methods of preparation, and applications in synthesis.
Syllabus
Learning and Teaching
Teaching and learning methods
Type | Hours |
---|---|
Revision | 10 |
Follow-up work | 67 |
Problem Classes | 9 |
Preparation for scheduled sessions | 40 |
Lecture | 24 |
Total study time | 150 |
Resources & Reading list
Textbooks
Gilchrist and Storr (1979). Orbital Reactions and Orbital Symmetry. Cambridge University Press.
A J Kirby (1996). Stereoelectronic Effects. OUP Oxford Chemistry Primers.
I. Fleming (2009). Molecular Orbitals and Organic Chemical Reactions Student Edition. Wiley.
F A Carey and R J Sundberg (1990). Advanced Organic Chemistry A and B. Oxford: Plenum.
Clayden, Greeves, Warren and Wothers (2001). Organic Chemistry. Oxford University Press.
I. Fleming (1976). Frontier Orbitals and Organic Chemical Reactions. Wiley.
I. Fleming (1998). Pericyclic Reactions. Oxford Chemistry Primers, OUP.
Assessment
Summative
This is how we’ll formally assess what you have learned in this module.
Method | Percentage contribution |
---|---|
Final Assessment | 100% |
Referral
This is how we’ll assess you if you don’t meet the criteria to pass this module.
Method | Percentage contribution |
---|---|
Final Assessment | 100% |