UNIT – I NOMENCLATURE OF ORGANIC COMPOUNDS, REACTIVEINTERMEDIATESAND ELECTRONIC EFFECTS:
Nomenclature of heterocyclics having not more than two hetero atoms such as oxygen, nitrogen and sulphur – Nomenclature of heterocyclic compounds of fused ring system -Nomenclature of alicyclic, bicyclic and tricyclic compounds.Reactive Intermediates: Classical and non classical carbocations, carbanions-free radicals, carbenes, nitrenes, arynes and singlet oxygen- general methods of generation,
detection, geometry, stability and reactivity of these intermediates. Electronic Effects: Inductive effect – resonance effect – hyper conjugation (Baker-Nathan effect) hydrogen bonding (inter and intramolecular) and steric effects.
UNIT – II METHODS OF DETERMINING REACTION MECHANISMS AND CORRELATION ANALYSIS
Kinetics and non-kinetic methods of determination of reaction mechanisms – Thermodynamic and kinetic aspects of organic reactions ,energy profile diagrams – spectroscopic studies, isotopic effects – intermediate versus transition states – product
analysis and its importance – crossover experiments-isotopic labelling studies. Correlation Analysis: Linear Free Energy Relations-Hammet equation – significance – sigma and rho applications and limitations – Taft, Swain-Scott-Grunwald-Winstein equations and their applications, classification of solvents.
UNIT – III STEREOCHEMISTRY I:
Optical isomerism – Optical activity and chirality – elements of symmetry – Stereochemistry of overcrowded molecules (hexahelicene, ansa compounds, cyclophanes and trans cycloalkenes -Newmann, Sawhorse and Fischer projections – representation and interconversion – Absolute configuration – R & S notations for special molecules(allenes, spirans, biphenyls)R-Snomenclature of cyclic chiral compounds –
molecules with more than one chiral center. Asymmetric synthesis – Optical puritydetermination of enantiomeric excess by NMR – definition of terms like prochirality,enantiotopicanddiastereotopic atoms, groups and faces – stereoselective and
stereospecific reactions.
UNIT – IV STEREOCHEMISTRY II:
Geometrical isomerism : E and Z nomenclature – determination of configuration of geometrical isomers (cyclisation, converting into compounds of known configuration, dipolemoment, converting into less symmetric compounds- spectroscopic methods)
configuration of cyclic and bicyclic ring systems – cis- trans nomenclature of three, four and six membered substituted cyclic systems-decalins. Dynamic Stereochemistry: Quantitative correlation between conformation and reactivity. Winstein-Eliel equation – Curtin- Hammet principle- conformation, reactivity and mechanism of cyclic systems and fused (decalin) ring systems-bridged(norbornane) systems-saponification of an ester – esterification of an alcohol – chromic acid oxidation of
cyclohexanols – neighbouring group participation – deamination of 2- amino cyclohexanol.
UNIT – V AROMATICITY AND REAGENTS IN ORGANIC SYNTHESIS:
Aromaticity: Aromatic character: Five-, six-, seven-, and eight-membered rings-other systems with aromatic sextets – Huckel’s theory of aromaticity,Craig’s rule- concept of homoaromaticity and antiaromaticity. – NMR concept of aromaticity and antiaromaticitynon benzeniod aromatic compounds- systems with 2,4,8 and 10 electrons, systems of more than 10 electrons (annulenes), Mobius aromaticity. alternant and non-alternant hydrocarbons (azulene type) – aromaticity in heteroaromatic molecules, sdnones and fullerenes. Reagents in organic synthesis: Oxidation: Baeyer-Villiger, Jacobsen epoxidation, Shi epoxidation, Jones reagent, DMP, TPAP, NOCl, Mn(OAc)3, Cu(OAC)2, Bi2O3,Swern oxidation. Reduction: Hydride transfer reagents from group III and group IV in reductions. (i) triacetoxyborohydride, L-selectride, K-selectride, Luche reduction (ii) stereo/enantioselectivity reductions (Chiral Boranes).