Principles of Organic Chemistry

Section A:

1. Electronic Theory of Organic Chemistry:

Atomic Theory, hybridisation, bonding, conjugation, delocalisation and resonance, homolysis and
heterolysis, electron availability in organic molecules, electron density, inductive and mesomeric
effects, hyperconjugation, electronic and classical steric effects.

2. Organic Acids and Bases:

Factors affecting acidity and basicity including structural and electronic considerations. Effects of
delocalisation and electronegativity on the basic nature of molecules containing lone pairs of
electrons.

3. Stereochemistry:

Conventions for drawing 3-D structures, dotted-line/wedge, sawhorse, and Newman conventions,
rotamers and potential-energy diagrams, staggered, eclipsed and gauche forms, ring systems, chair
and boat forms of cyclohexane, axial and equatorial substituents, bond angle strain, transannular
interactions, other ring systems, cyclopentane, cyclobutane and cyclopropane.

4. Stereoisomerism:

Chiral molecules, asymmetric carbon atoms, enantiomers, chirality in nature, examing a molecule for
chirality, optical activity and its detection using plane-polarised light, specific rotation, dextro- and
levorotatory molecules, racemates, enantiomeric purity, absolute configuration and the R/S (CIP)
sequence rules for nomenclature, Fisher projections and their use and manipulation, diastereomers,
tartaric acid, meso compounds, resolution of enantiomers - chemical and physical methods.

5. Stereochemical aspects of organic reactions:

Retention, inversion, racemisation, enantiotopic and diastereotopic atoms and faces, asymmetric
synthesis.

6. Optical activity in molecules possessing no chiral centres:

Allenes, biphenyls and related structures.

Section B:

1. Nucleophilic Substitution Reaction:

SN1 and SN2 reactions: Kinetic evidence; stereochemical implications of mechanism: Walden
inversion; SNi and retention of configuration.

2. Elimination Reactions:

E1, E2 and E1cB reactions; factors favouring one type of mechanism over the other, stereochemistry
of E2 reactions: SYN- and ANTI-elimination; elimination vs substitution.

3. Electrophilic and Nucleophilic Addition to C=C Bond:

E/Z convention for double bond compounds; Anti addition and halonium intermediates,
Markownikov's Rule and the peroxide effect, hydroboration; addition to conjugated dienes: Diels
Alder reaction (pericyclic mechanism).

Nucleophilic addition: Michael reaction; 1,4-addition to αb -unsaturated carbonyl groups.

4. Nucleophilic Addition to C=O Bonds:

Electronic and steric effects and acid/base catalysis of carbonyl

addition reactions. Hemi-acetal, acetal and ketal formation and other additions including those
involving metallohydrides and alkoxides; Cannizzaro reaction,pinacol formation and rearrangement;
condensation reactions of aldehydes and carboxylic derivatives; addition of carbanions, including
aldol type reactions: Claisen-Schmidt,

Perkin etc., benzoin condensation.

5. Free Radical Mechanisms:

Factors affecting the stability of free radicals. Formation of free radicals. Reactions: initiation,
propagation and termination modes of chain reactions. Important free radical reactions, including
allylic bromination by NBS.