Module Details

The information contained in this module specification was correct at the time of publication but may be subject to change, either during the session because of unforeseen circumstances, or following review of the module at the end of the session. Queries about the module should be directed to the member of staff with responsibility for the module.
Code CHEM333
Coordinator Dr RP Bonar-Law
Year CATS Level Semester CATS Value
Session 2016-17 Level 6 FHEQ First Semester 15

Pre-requisites before taking this module (or general academic requirements):

Completion of years 1 and 2 of an MChem or BSc (Hons) Chemistry programme or, for PGT students, a non-University of Liverpool BSc (Hons) Chemistry programme.  


The aim of the course is to extend second year knowledge of synthetic and physical organic chemistry.

Learning Outcomes

By the end of the module, students should:

  • Have a good understanding of modern synthetic reactions and their mechanisms.
  • Be able to deduce mechanisms on the basis of kinetic and other evidence.

Teaching and Learning Strategies

Lecture -

Tutorial -


Organic synthesis and reactions (20 lectures)
Pericyclic reactions 1: cycloadditions
The rules that govern cycloadditions
Photochemical reactions: reactions that need light
Making six-membered rings by the Diels–Alder reaction< /span>
Making four-membered rings by [2 + 2] cycloaddition
Making five-membered rings by 1,3-dipolar cycloaddition
Using cycloaddition to functionalize double bonds stereospecifically
Using ozone to break C=C double bonds
Pericyclic reactions 2: Sigmatropic and electrocyclic reactions
Stereochemistry from chair-like transition states
Making γ,δ-unsaturated carbonyl compounds
What determines whether these pericyclic reactions go ‘forwards’ or ‘backwards’
Fischer Indole synthesis
Why substituted cyclopentadienes are unstable
What ‘con’ and ‘dis’-rotatory mean
Reactions that open small rings and close larger rings
Rearrangements and Fragmentations
Participation means acceleration and retention of stereochemistry and may mean rearrangement
Participating groups can have lone pairs or π-electrons
Carbocations often rearrange by alkyl migration
Ring expansion by rearrangement
Using rearrangements in synthesis
Electron donation and electron withdrawal combine to create molecules that fragment
Anti-periplanar conformation is essential
Small rings are easy to fragment, medium and large rings can be made in this way
Double bond geometry can be controlled
Using fragmentations in synthesis
Radical reactions
Radical reactions follow different rules to those of ionic reactionsBond strength is very important
Radicals can be formed with Br, Cl, Sn, and Hg
Efficient radical reactions are chain reactions
There are electrophilic and nucleophilic radicals
Radicals favour conjugate addition
Cyclization is easy with radical reactionsDissolving metal reductions with metal-ammonia systems applied to aromatic systems (Birch reduction) and enones and their synthetic applications. Dissolving metal reductions applied to carbonyl groups - Pinacol coupling and acyloin condensation.
Wittig, Wittig-Horner and Wadsworth-Emmons reactions and their use in synthesis. Aza-Wittig reaction.Mitsunobu reaction, mechanism and applications.
Introduction to organosulfur compounds (oxidation states, names etc.). Synthesis and chemistry of sulfoxides, allylic sulfoxide-sulfenic ester rearrangement. Pummerer reaction, syn elimination of sulfoxides.
Julia reaction, Ramberg Backlund reaction and extrusion of SO2 from sulfolenes. Chemistry of sulfur ylids, Corey/Trost reagents.
Comparison of sulfur and selenium compounds. Reactions of selenoxides, syn elimination and [2,3] sigmatropic rearrangements. Oxidation reactions of selenium dioxide. Selenium mediated cyclisation reactions (PhSeCl etc.).
Physical organi c chemistry (11 lectures)
Equilibria, transition states and rates
Free energy diagrams, transition states, connection between equilibrium and rate constants K = k1/k-1, Hammond’s postulate, thermodynamic vs kinetic control, Curtin-Hammett.      
Revision of elementary kinetics, steady state for multistep reactions, primary deuterium kinetic isotope effect.        
SN2, SN1
Mostly revision of year 2 material
Elimination reactions
Revision of E1, E2, E1cb, kinetics, mechanistic continuum     
Addition reactions
Revision of HX, X2 additions with kinetics, some synthetic applications
Nucleophilic substitution at ca rbonyls
Tetrahedral intermediates and mechanisms for ester hydrolysis.
The Hammett equation    
Substituent constants, reaction constants, correlation of rates and equilibria, multistep reactions, physical basis of LFER.

Recommended Texts

Reading lists are managed at Click here to access the reading lists for this module.
Explanation of Reading List:

Teaching Schedule

  Lectures Seminars Tutorials Lab Practicals Fieldwork Placement Other TOTAL
Study Hours 37


Timetable (if known)              
Private Study 108


EXAM Duration Timing
% of
Penalty for late
Unseen Written Exam  3 hours  1st Semester  80  Yes  Standard UoL penalty applies  Assessment 2 Notes (applying to all assessments) Assignments: This work is not marked anonymously. August resit for PGT students if applicable. Integrated Master's students resit at the next normal opportunity.  
CONTINUOUS Duration Timing
% of
Penalty for late
Coursework  5x1 hour problem set  1st Semester  20  No reassessment opportunity  Standard UoL penalty applies  Assessment 1 There is no reassessment opportunity,