Module Catalogues, Xi'an Jiaotong-Liverpool University   
 
Module Code: CHE303
Module Title: Advanced Organic Chemistry
Module Level: Level 3
Module Credits: 5.00
Academic Year: 2020/21
Semester: SEM1/SEM1
Originating Department: Chemistry
Pre-requisites: N/A
   
Aims
The aim of the course is to consolidate and extend second year knowledge of synthetic and physical organic chemistry, and introduce some aspects of C-C formation catalyzed reactions.
Learning outcomes 
A have a good understanding of pericyclic reactions

B understand radical reactions

C understand how to control double bond geometry

D be able to deduce mechanisms on the basis of kinetic and other evidence

E understand catalyzed carbon-carbon bond formation

Method of teaching and learning 
Lectures and tutorials
Syllabus 
• Pericyclic reactions:

o cycloadditions • The rules that govern cycloadditions • Photochemical reactions: reactions that need light • Making six-membered rings by the Diels–Alder reaction • 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

o 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

o Rarrangements 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 reactions • Bond 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 reactions • Dissolving 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.

• Synthesis of alkenes -- controlling double bond geometry • Stereospecific eliminations reactions. • Wittig, Peterson and Julia reactions • Reduction of alkynes

• Physical organic chemistry • Revision of basic mechanisms • Equilibrium and rates (Revision of basic thermodynamics; Acid-base equilibria; pKa of common acids; Reaction coordinate; transition state; microscopic reversibility; Connection between equilibrium and rate constants) • Rates, Equilibria and Free Energy Diagrams (Hammond's postulate; thermodynamic vs. kinetic control; Curtin-Hammett principle) • Kinetics (Revision of elementary kinetics; Multistep reactions, bottlenecks, rate determining step and steady state approximation, connection with free energy diagrams; Primary deuterium kinetic isotope effect)

• Catalysed C-C bond formation

o Suzuki, Stille coupling reactions
Delivery Hours  
Lectures Seminars Tutorials Lab/Prcaticals Fieldwork / Placement Other(Private study) Total
Hours/Semester 26     13      111  150 

Assessment

Sequence Method % of Final Mark
1 Final Exam 70.00
2 Coursework 15.00
3 Class Test 15.00
1 Final Exam 70.00
2 Coursework 15.00
3 Class Test 15.00

Module Catalogue generated from SITS CUT-OFF: 6/5/2020 5:15:17 PM