UNIVERSITY OF WARWICK

Proposal Form for New or Revised Modules (MA1- version 4)

Approval information /
Approval Type / New module Revised module
Discontinue module
Date of Introduction/Change / October 2012
If new, does this module replace another? If so, enter module code and title:
If revised/discontinued, please outline the rationale for the changes: / Addition of F108 degree stream as taking the module in year 4. Also then subsequently added BF91 and B9F1 as core. Section 11.
Confirmation that affected departments have been consulted: / N/A
Module Summary /
1. Module Code (if known) / CH3E4
2. Module Title / Stereoselective Synthesis
3. Lead department: / Chemistry
4. Name of module leader / Dr David Fox (and Prof Martin Wills)
5. Level / UG: Level 4 (Certificate) Level 5 (Intermediate)
Level 6 (Honours)
PG: Level 7 (Masters) Level 8 (Doctoral)
See Guidance Notes for relationship to years of study
6. Credit value(s) (CATS) / 7.5 CATS
7. Principal Module Aims / By the end of their second year of studies, undergraduate students have learnt many of the key transformations of organic chemistry. They are equipped with the ability to design synthetic approaches to complex organic molecules and to identify which key bond-forming reactions are required. This course extends this knowledge to the more complex and challenging area of stereoselective and asymmetric synthesis, which refers to the specific three dimensional shape and structure of specific target molecules. By the end of this course, students shall understand how to control the absolute and relative configuration of organic molecules during their synthesis.
Trained chemists working in industry and academia are frequently required to design and execute total syntheses of complex target molecules. A pivotal objective of our degree course is to equip all our graduates with the ability to do this to a high standard. This course addresses the key issues of stereochemical control associated with organic synthesis.
8. Contact Hours (summary) / 15hrs (3 per week) Lectures
2 hrs Workshops
9. Assessment methods (summary) / 100% Examination
100% Assessed Visiting Students Only
Module Context /
10. Please list all departments involved in the teaching of this module. If taught by more than one department, please indicate percentage split.
Chemistry
11. Availability of module
Degree Code / Title / Study Year / C/OC/
A/B/C / Credits
F100 / Chemistry BSc / 3 / Core / 7.5
F101 / Chemistry BSc with Intercalated Year / 4 / Core / 7.5
F102 / General Chemistry BSc / 3 / Option / B / 7.5
F105 / Chemistry MChem / 3 / Core / 7.5
F106 / Chemistry MChem with Professional Experience / 3 / Core / 7.5
F107 / Chemistry MChem with Intercalated Year / 3 or 4 / Core / 7.5
F108 / Chemistry MChem with Industrial Training / 4 / Core / 7.5
F121 / Chemistry with Medicinal Chemistry BSc / 3 / Core / 7.5
F122 / Chemistry with Medicinal Chemistry with Intercalated Year BSc / 4 / Core / 7.5
F125 / Chemistry with Medicinal Chemistry MChem / 3 / Core / 7.5
F126 / Chemistry with Medicinal Chemistry with Professional Experience MChem / 3 / Core / 7.5
F127 / Chemistry with Medicinal Chemistry MChem with Intercalated Year / 3 or 4 / Core / 7.5
BF91 / Biomedical Chemistry BSc / 3 / Core / A / 7.5
B9F1 / Biomedical Chemistry BSc with Intercalated Year / 4 / Core / A / 7.5
FC11 / Chemical Biology MChem / 3 / Option / A / 7.5
F1C1 / Chemical Biology MChem with Intercalated Year / 3 or 4 / Option / A / 7.5
Visiting Students / 7.5
12. Minimum number of registered students required for module to run
10
13. Pre- and Post-Requisite Modules
Pre-Requisites
CH248, CH264
Post-Requisites
CH402
Module Content and Teaching /
14. Teaching and Learning Activities
Lectures / 15 hrs total (3 per week)
Workshops / 2 hrs total
Tutorials
Laboratory sessions
Total contact hours / 17 hrs
Module duration (weeks) / 5 weeks
Other activity
(please describe): e.g. distance-learning, intensive weekend teaching etc. / Self Study 58 hrs
15. Assessment Method (Standard)
Type of assessment / Length / % weighting
Examinations / 1.5 Hours / 100%
Assessed essays/coursework / Words
Other formal assessment / Visiting Students AO and VA Assessment / 100%
16. Methods for providing feedback on assessment.
Marks for Examination to be provided via Personal Tutor.
17. Outline Syllabus
Understand basic concepts of stereoselective and asymmetric synthesis by using common successful examples of oxidations, reductions, and C-C bond forming reactions (e.g. enolate alkylations, aldols, conjugate additions, cycloadditions, additions to aldehydes and ketones)
Influence of sterics and stereoelectronics
1) Diastereoselective synthesis- substrate controlled reactions
a) Nucleophilic additions to a-chiral and b-chiral carbonyls
1,2-induction - Felkin, polar Felkin and chelated-Felkin models
1,3-induction – dipole controlled addtions b-alkoxy carbonyls and chelation and non-chelation control e.g. 1,3 diol formation
b) Electrophilic additions to a-chiral alkenes
Houk control in hydroborations, cyclopropanations, epoxidations and dihydroxylations.
SE2’ reactions of chiral allyl silanes
Chelation controlled reactions
2) Synthesis of enantiomerically enriched compounds
a) The Chiral Pool
Reactions strting with hydroxy-acids, amino-acids, amino-alcohols, carbohydrates, terpenes
b) Chiral Resolution
Non-dynamic and dynamic chrial resolution using diastereoisomeric salts and inclusion complexes.
Synthesis and separation of enantiomers via diastereoisomers
Asymmetric synthesis of phosphines via resolution od intermediates
c) Chiral auxiliaries (substrate control)
chiral enolates e.g. glycine anion equivalents, Williams amino acid template.
chiral enolates Evans auxiliary alkylation and aldols, conjugate additions, Diels Alder reactions
d) Chiral reagents (reagent control)
Carbonyl additions e.g. , BINAL, terpene-borane reductions, hydroboration, boron-allylation
Chiral deprotonation.
e) Asymmetric catalysis (reagent control)
Sharpless asymmetric dihydroxylation (AD) and aminohydroxylation (AA)
Asymmetric hydrogenation of C=C and C=O bonds using Rh, Ru and Ir reagents with enantiomerically-pure ligands. Catalyst based DKR e.g. Noyori Hydrogenation of -ketoesters.
Asymmetric transfer hydrogenation of C=O and C=N bonds using organometallic and organocatalytic methods (Chiral Bronstead acid catalysis).
Organocatalytic reductions of C=C bonds in enones. Additions to carbonyls, reductions (Noyori).
Enolate chemistry; aldol reactions and related additions (i.e.. organocatalytic), Mukayama aldol.
Cycloadditions (organometallic and organocatalytic methods).
Pd catalysed allylation reactions.
Includes examples of catalysts and reactions.
f) Enzymes
Esterification and hydrolysis with lipases ad esterases
includes Dynamic Kinetic Resolution of alcohols via epimierisation.
Asymmetric oxidations e.g. of C-N bonds and Baeyer-Villiger.
Includes examples of catalysts and reactions.
18. Illustrative Bibliography

Recommended Reading for 7.5 CATS module

1.  Organic Chemistry J. Clayden, N. Greeves, S. Warren, P. Wothers OUP, 2001 [CGWW].
2.  Organic Synthesis – Strategy and Control P. Wyatt and S. Warren, Wiley 2007
Further reading
3. Stereochemistry at a Glance J. Eames and J. M. Peach, Blackwell, 2003.
4. Guide to Organic Stereochemistry S. R. Buxton, S. M. Roberts, Longman, 1996, QD1858.B8.
6. Advanced Organic Chemistry, J. March, 4th Edn., Wiley, 1992, QD 1722.M2.
7. Alicyclic Chemistry, F. J. McQuillan, 2nd Edn., Cambridge, 1983, QD 2310.M2.
8. Stereochemistry of Organic Compounds E. L. Eliel, S. H. Wilen, L. N. Mander Wiley, 1994, QD1858.E5.
9. Catalysis in Asymmetric Synthesis’ by V. Caprio and J. M. J. Williams, Wiley, 2010 (2nd Edition).
10. Asymmetric Catalysis in Organic Synthesis; Noyori, R.; John Wiley and Sons Ltd; NY, 1994.
11. Catalytic Asymmetric Synthesis,; Ojima, I. Ed.; VCH Press; Berlin, 1993, now updated in 2000.
12. Comprehensive Asymmetric Catalysis I-III / Eric N. Jacobsen, Andreas Pfaltz, Hisashi Yamamoto (eds.), 1999.
13. Metal-free organic catalysts in asymmetric synthesis / Albrecht Berkessel: Wiley-VCH, 2003.
19. Learning outcomes
Successful completion of the module leads to the learning outcomes. The learning outcomes identify the knowledge, skills and attributes developed by the module.
Learning Outcomes should be presented in the format ”By the end of the module students should be able to...” using the table at the end of the module approval form:
Resources /
20. List any additional requirements and indicate the outcome of any discussions about these.
Approval /
21. Module leader’s signature / Dr David Fox
22. Date of approval / 5th December 2011, then 6th Feb for additional BF91 and BF91 change
23. Name of Approving Committee (include minute reference if applicable) / LTC
24. Chair of Committee’s signature / Dr Andrew Clark
25. Head of Department(s) Signature / Prof Mike Shipman
Examination Information /
A1. Name of examiner (if different from module leader) / Dr David Fox
A2. Indicate all available methods of assessment in the table below
% Examined / % Assessed by other methods / Length of examination paper
100% / 1.5
A3. Will this module be examined together with any other module (sectioned paper)? If so, please give details below.
Examined with CH3E5 on paper CH3CHE
A4. How many papers will the module be examined by? / 1 paper 2 papers
A5. When would you wish the exam take place (e.g. Jan, April, Summer)? / March
A6. Is reading time required? / Yes No
A7. Please specify any special exam timetable arrangements.
A8. Stationery requirements
No. of Answer books?
Graph paper?
Calculator?
Any other special stationery requirements (e.g. Data books, tables etc)?
A9. Type of examination paper
Seen? / Yes No
Open Book? / Yes No
Restricted? / Yes No
If restricted, please provide a list of permitted texts:

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LEARNING OUTCOMES /
(By the end of the module the student should be able to....) / Which teaching and learning methods enable students to achieve this learning outcome?
(reference activities in section 15) / Which summative assessment method(s) will measure the achievement of this learning outcome?
(reference activities in section 16) /
1) Understand how reactions can form different stereoisomers of products / Lectures and workshops. / Formative and summative assessment by examination
2) Building on CH264, be able to draw simple transition-states in 3 dimensions / Lectures and workshops. / Formative and summative assessment by examination
3) Successfully predict simple aldol stereochemistry based on metals and enolate geometry / Lectures and workshops. / Formative and summative assessment by examination
4) Use facial steric arguments to predict stereochemical outcome / Lectures and workshops. / Formative and summative assessment by examination
5) Use stereoelectronic arguments (e.g. Houk’s rule) to predict stereochemical outcome. / Lectures and workshops. / Formative and summative assessment by examination
6) Understand basics of chiral resolution via diastereoisomer formation / Lectures and workshops. / Formative and summative assessment by examination
7) Identify useful amino acids and know how they can be turned into chiral auxiliaries and templates. / Lectures and workshops. / Formative and summative assessment by examination
8) Explain and predict the stereochemical outcome of Evans alkylations, aldols, conjugate additions and cycloadditions. / Lectures and workshops. / Formative and summative assessment by examination
9) Explain and predict the stereochemical outcome of chiral reagent controlled reactions such as terpene / borane mediated reductions and additions. / Lectures and workshops. / Formative and summative assessment by examination
10) Understand and predict outcome of AE and AD mechanism (with help of mnemonics) / Lectures and workshops. / Formative and summative assessment by examination
11) Understand and predict outcome of organocatalysed iminium and enamine mediated reactions e.g. aldols and cycloadditions. / Lectures and workshops. / Formative and summative assessment by examination
12) Understand basis of kinetic resolution and be able predict reaction outcomes. / Lectures and workshops. / Formative and summative assessment by examination
13) Understand basis of dynamic kinetic resolution. / Lectures and workshops. / Formative and summative assessment by examination
14) Understand concepts behind asymmetric enzyme catalysed processes and use them to predict reaction products / Lectures and workshops. / Formative and summative assessment by examination

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