Unit 1

Basic concepts
Acids and Bases – Acidity – pKa, basicity. Factors influencing acidity and basicity, HSAB principle. Electron displacement effects – resonance, inductive, electromeric, mesomeric and hyper conjugative effects. Reactive intermediates – generation, structure and reactivity reactions and rearrangement involving of carbocations, non-classical carbocations, carbanions, carbon radicals, radical ions, carbenes, nitrenes, isonitrenes, arynes and Bunte salt.

Unit 2

Aromaticity
Criteria for aromaticity – energy, structural and electronic criteria for aromaticity – relationship among them. Aromatic, antiaromatic and homoaromatic compounds. Aromaticity in annulenes, polycyclic compounds, charged rings – aromatic cations and anions, fused rings. Heteroaromatic systems.

Unit 3

Strain and Stability
Thermochemistry of stable molecules – thermochemistry of reactive intermediates. Relationships between structure and energetics. Electronic effects, highly-strained molecules, long bonds, small rings, large rotation barrier and molecular mechanics.

Unit 4

Energy Surfaces and Kinetic Analyses
Reaction coordinate diagram, activated complex, transition state theory, Arrhenius rate law. Boltzmann distributions, activation parameters, Hammond postulate, Curtin-Hammett principle, microscopic reversibility. Kinetic vs. thermodynamic control, kinetic experiments. Baldwin rules. Kinetic analysis of simple and complex mechanisms, steady state and saturation kinetics, methods to follow kinetics, calculating rate constants, Marcus theory and multiple reaction coordinates.

Unit 5

Linear free energy relationship
Isotope effects, substituent effects, linear free energy relationship (LFER), Hammet plots, steric and polar effects – Taft parameters. Solvent effects-Grunwald-Weinstein plots, Schleyer adaptation, acid base effects and conditions to create LFER.

Prerequisite: None, but this course is a prerequisite for Principles of Organic Chemistry, Organic Synthesis I and II.

1. Modern Physical Organic Chemistry: E. Anslyn and D.A. Dougherty (2006) 1st edition, University Science Books.
2. Organic Chemistry: J. Clayden, N. Greeves, S. Warren and P. Wothers (2012) 2nd edition, Oxford University Press.
3. Advanced Organic Chemistry: Part A: Structure and Mechanism: R.J. Sundberg and F.A. Carey (2007) 5th edition, Kluwer/Plenum Press.
4. Physical Organic Chemistry: N. Isaacs (1995) 2nd edition, Addison-Wesley-Longman.
5. March’s Advanced Organic Chemistry: M. Smith and J. March, 6th edition, Wiley-Interscience.