Knowledge and understanding: the main goal is to furnish to the student the tools for the comprehension and the dissertation of the reaction mechanisms in organic chemistry; particular attention will be paid to the influence of the reaction medium and catalyst on the reactive processes.
Learning skills: students will acquire the specific language of the reaction mechanism field and will achieve the ability to correlate the various aspects of the arguments faced during the whole course.
Knowledge of the concepts developed in the Organic Chemistry 1 and Organic
Chemistry 2 courses
Course contents summary
At first the principal kinetic equations and primary and secondary isotope effects will be examined
Then, the Hammet’s equation (and its modifications) will be exposed, to connect the structural effects to reactivity of organic compounds
Furthermore, the role of the solvent and of acid and base catalysts on various reactions will be examined.
Concerning reaction intermediates, those of radical nature will be in described in detail.
Finally intramolecular catalysis will be thouroughly discussed.
Summary of the principal kinetic equations
Stoichiometry and reaction order. Reversible and consecutive reactions. Stationary
State Approximation. Saturation kinetics. Parallel reactions. Primary and secondary
isotopic kinetic effects.
Structural effects on the reactivity of organic compounds.
The Hammett equation and his modifications. The Yukawa-Tsuno equation.
Separation of polar, resonance and steric effects. The Taft equation.
Solvent effect on the reactivity of organic compounds.
Salt effect. The Ingold solvent effect. Thermodynamic aspects of the solvent effect.
Specific salvation. Donor and acceptor solvents. Solvent effect empiric parameters:
Z, Et(30), Y.
Brönsted Acids and Bases and Catalysis
Acidity and basicity functions. Superacids media. Acidity and basicity scales in
different solvents and in gas phase. Acid-base catalysis in bioorganic systems.
Proton transfer reactions. The Brönsted relation.
Reaction intermediates and their study
Isolation, trapping and study of reaction intermediaets. Free radical classification.
Free radical sources. The capto-dativo effect. Radical inhibitors. Nucleophilic and
electrophilic free radicals. Organic synthesis through free radicals.
Cycle formation reactions and intramolecular catalysis. Vicinal groups participation and intramolecular catalysis. Kinetic and thermodynamic
aspects of cycle formation reactions.
Eric V. Anslyn, Dennis A. Daugherty: Modern Physical Organic Chemistry,
University Science Books, 2006
F.A. Carey e R.J. Sundberg Advanced Organic Chemistry 4a Edizione, Plenum
J. March Advanced Organic Chemistry Reactions, Mechanisms, and Structure , 5a
Edizione John Wiley & Sons , 2000