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 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,  nitren, 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, alkyledines, cycloalkyledines, spiranes, ansa compounds , 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 trisubstituted), cyclohexenes, cyclohexanones, halocyclohexanones, decalins, decalols and decalones, effect of conformation on reactivity, strain in cycloalkanes.

Chiral synthesis, Steroselective 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 auxillary and chiral pool.