UNIVERSITY OF WARWICK
Proposal Form for New or Revised Modules (MA1- version 4)
Approval information
Approval Type
Date of
Introduction/Change
New module
Discontinue module
Revised module
October 2012
If new, does this module
replace another? If so,
enter module code and
title:
If revised/discontinued,
Addition of F108 degree stream as taking the module in year 4.
please outline the rationale Also then subsequently added BF91 and B9F1 as core. Section 11.
for the changes:
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:
PG:
Level 4 (Certificate)
Level 6 (Honours)
Level 7 (Masters)
Level 5 (Intermediate)
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
1
Module Summary
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
2
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
F100
F101
F102
F105
F106
F107
F108
F121
F122
F125
F126
F127
BF91
B9F1
FC11
F1C1
Title
Study Year
C/OC/
A/B/C
Chemistry BSc
Chemistry BSc with Intercalated Year
General Chemistry BSc
Chemistry MChem
Chemistry MChem with Professional
Experience
Chemistry MChem with Intercalated Year
Chemistry MChem with Industrial Training
Chemistry with Medicinal Chemistry BSc
Chemistry with Medicinal Chemistry with
Intercalated Year BSc
Chemistry with Medicinal Chemistry
MChem
Chemistry with Medicinal Chemistry with
Professional Experience MChem
Chemistry with Medicinal Chemistry
MChem with Intercalated Year
Biomedical Chemistry BSc
Biomedical Chemistry BSc with Intercalated
Year
Chemical Biology MChem
Chemical Biology MChem with Intercalated
Year
Visiting Students
3
4
3
3
3
Core
Core
Option
Core
Core
3 or 4
4
3
4
Core
Core
Core
Core
7.5
7.5
7.5
7.5
3
Core
7.5
3
Core
7.5
3 or 4
Core
7.5
3
4
Core
Core
A
A
7.5
7.5
3
3 or 4
Option
Option
A
A
7.5
7.5
Credits
7.5
7.5
B 7.5
7.5
7.5
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)
3
Module Content and Teaching
Workshops
Tutorials
Laboratory sessions
Total contact hours
Module duration (weeks)
Other activity
2 hrs total
17 hrs
5 weeks
Self Study 58 hrs
(please describe): e.g.
distance-learning, intensive
weekend teaching etc.
15. Assessment Method (Standard)
Type of assessment
Examinations
Assessed
essays/coursework
Other formal assessment
Length
1.5 Hours
Words
% weighting
100%
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 -chiral and -chiral carbonyls
1,2-induction - Felkin, polar Felkin and chelated-Felkin models
1,3-induction – dipole controlled addtions -alkoxy carbonyls and chelation and non-chelation control e.g.
1,3 diol formation
b) Electrophilic additions to -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
4
Module Content and Teaching
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
-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
5
Module Content and Teaching
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
6
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
100%
Length of examination paper
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?
A5. When would you wish
the exam take place (e.g.
Jan, April, Summer)?
1 paper
2 papers
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:
7
LEARNING OUTCOMES
(By the end of the module the student should be able
to....)
1) Understand how reactions can form different
stereoisomers of products
2) Building on CH264, be able to draw simple transitionstates in 3 dimensions
3) Successfully predict simple aldol stereochemistry based
on metals and enolate geometry
4) Use facial steric arguments to predict stereochemical
outcome
5) Use stereoelectronic arguments (e.g. Houk’s rule) to
predict stereochemical outcome.
6) Understand basics of chiral resolution via diastereoisomer
formation
7) Identify useful amino acids and know how they can be
turned into chiral auxiliaries and templates.
8) Explain and predict the stereochemical outcome of Evans
alkylations, aldols, conjugate additions and cycloadditions.
9) Explain and predict the stereochemical outcome of chiral
reagent controlled reactions such as terpene / borane
mediated reductions and additions.
10) Understand and predict outcome of AE and AD
mechanism (with help of mnemonics)
11) Understand and predict outcome of organocatalysed
iminium and enamine mediated reactions e.g. aldols and
cycloadditions.
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)
Lectures and workshops.
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Lectures and workshops.
Lectures and workshops.
Lectures and workshops.
Lectures and workshops.
Lectures and workshops.
Lectures and workshops.
Lectures and workshops.
Lectures and workshops.
Lectures and workshops.
Lectures and workshops.
Formative and summative assessment by
examination
Formative and summative assessment by
examination
8
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)
12) Understand basis of kinetic resolution and be able
predict reaction outcomes.
13) Understand basis of dynamic kinetic resolution.
Lectures and workshops.
14) Understand concepts behind asymmetric enzyme
catalysed processes and use them to predict reaction
products
Lectures and workshops.
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Formative and summative assessment by
examination
Lectures and workshops.
9