STRUCTURE, REACTIVITY AND STEREOCHEMISTRY OF ORGANIC COMPOUNDS

Aromaticity in benzenoid and non-benzenoid compounds, alternant and non-alternant hydrocarbons, Huckel’s rule and Möbius system, energy level of π molecular orbitals in three to eight membered monocyclic systems having conjugation, annulenes, fullerenes, antiaromaticity, homoaromaticity, PMO approach, steric inhibition to resonance.

Bonds weaker than covalent: Addition compounds, phase transfer catalysis and crown ethers, cryptands, inclusion compounds, cyclodextrins, catenanes, rotaxanes and kekulene, H-bonding and its effect on organic compounds.

A review of types of mechanisms and reactions: methods of determining reaction mechanism, thermodynamic and kinetic control of reactions, Hammond’s postulate, Curtin- Hammett principle, isotope effects.

Effect of structure on reactivity, resonance effect, field effects & steric effects, quantitative treatment of the effect of structure on reactivity, the Hammet equation and linear free energy relationship, substituent and reaction constants & Taft equation.

Applications of HSAB principle to organic reactions.

Types, generation, structure, stability, detection and reactivity of the reactive intermediates: carbocation including non-classical carbocation, carbanion, free radical, radical anion, carbene,  nitrene, benzyne, nitrenium ion, electrophiles and nucleophiles,molecular rearrangements involving above intermediates viz. Wagner - Meerwein, Pinacol-Semipinacol, Benzil-Benzilic acid, Hoffmann, Curtius, Lossen, Schmidt, Beckmann, Naber, Favorskii, Wittig,  Riemer–Tiemann reaction,dissolving metal reduction.

Chirality and asymmetry, molecules with one, two or more chiral centres,configuration nomenclature, D/L and R/S types of recemates and methods of resolution.

Prochirality: Topicity of ligands and faces and their nomenclature, stereogenicity, pseudoasymmetry, planar chirality, axial chirality, optical purity, chirogenicity, stereogenic and prochiral centres, optical activity in the absence of chiral carbons: biphenyls, allenes, alkyldienes, cycloalkyldienes, spiranes, ansacompounds, adamantanes, and cyclophanes, chirality due to helical shape (P & M), chirality in the compounds containing N, S and P.

Configurations, conformations and stability of cyclohexanes (mono-, di-, and tri-substituted), cyclohexenes, cyclohexanones, halocyclohexanones, decalins, decalols and decalones, effect of conformation on reactivity, strain in cycloalkanes.

Chiral synthesis, stereoselective and stereospecific synthesis, Prelog’s rule, Felkin-anh rule, CD, ORD, octant rule, Cotton effect and their application in determination of absolute and relative configuration and conformation, the axial haloketone rule,chiral auxiliary and chiral pool.