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 Course Module: Organic Reaction Mechanisms
   
 
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 Module Code:  CM322

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Course Outline
   
Introduction to mechanism in organic and biological chemistry; reactive
intermediates (1 L)
   
Carbocations, structure and mechanism, generation and rearrangements. NMR
of carbocations in superacids. Stability of carbocations - resonance,
aromaticity, substituent and steric effects. Rearrangements, neighbouring
group participation; cyclopropyl, aryl, acetoxy groups. Principles and
concepts in mechanistic studies :- primary kinetic isotope effects, linear
free energy relationships, resonance and inductive effects, steric effects,
secondary kinetic isotope effects, hyperconjugation, stereoelectronic
effects, aromatic character, ring strain, non-bonded interactions,
transannular effects, thermodynamic stability. (4L)
   
Carbenes and nitrenes, generation, reactions and rearrangements. Thermal
rearrangements of carbenes. Singlet and triplet species. (2L)
   
Free radicals; generation and reactions. Free radical chain reactions.
Organotin and Barton methods of generating radicals for organic synthetic
reactions. Free radical cyclizations and fragmentations. Domino
cyclizations and fragmentations. Radical clocks - cyclopentyl and
cyclopropylcarbinyl systems. Enediynes to diradicals, natural enediynes,
synthetic analogues as potential drugs (4L)
   
Selected enzymatic reactions. Cytochrome P450 systems. Aromatase -
aromatization of ring A of steroids. Cyclooxygenase - arachidonic acid to
prostanoids and leukotrienes. b-Lactam biosynthesis - mechanistic studies
with isopenicillin N-synthase. Radicals in biology (4L)