Advanced organic chemistry and mechanism investigation textbooks.
P. Sykes, A guide book to Mechanism in Organic Chemistry, Longman
F. A. Carey, R. J. Sundberg, Advanced Organic Chemistry , Part A, Kluwer Academic/Plenum Publishers
G.B. Gill, M. R. Willis, Pericyclic Reactions, Chapman and Hall
T. L. Gilchrist, R. C. Storr, Organic Reactions and Orbital Symmetry, Cambridge University Press
I. Fleming, Frontier Orbitals and Organic Chemistry Reactions, Wiley-Interscience
Learning Objectives
•Knowledge and comprehension.
•Ability to apply knowledge and comprehension.
Knowledge of the basic concepts for the study of the reaction mechanism in organic chemistry.
Applications of the methods for mechanistic investigation to the study of some classes of organic reactions.
Foreseeing the mechanistic pathway of some organic reactions, the nature of the reaction products and the selectivities.
Prerequisites
Courses to be used as requirements (required and/or recommended)
Required courses: none
Recommended courses: none
Teaching Methods
Frontal lectures: 48 hours
Type of Assessment
Opportunity for an intermediate written examination on the first part of the course (general methods for organic reactions mechanism investigation) is offered and it may be used as part of the final examination.
Oral final examination.
Assessment of the comprehension of the treated subjects, ability of critical reasoning, quality of the presentation.
There are at least 8 examination sessions, especially in February, June, July, and September.
Registration on line is necessary to take the examination. The sessions for the academic year 2016/2017 are available at the link: https://sol.unifi.it/docprenot/docprenot
Course program
Investigation of organic reactions mechanism. Reaction energy profiles. Kinetic and thermodynamic control. Hammond’s postulate. Curtin-Hammett principle. Kinetic studies. Rate-limiting step, reaction order and molecolarity. Steady state approximation. Isotopic labelling. Kinetic isotope effects. Reaction intermediates. Linear free energy relationships. Hammett equation. Upwards and downwards deviations. Mechanistic study of some classes of organic reactions. Molecular rearrangements. Elimination processes: classification and mechanistic hypotheses, reactivity, stereochemical outcome, regio- and stereo-selectivities. Nucleophilic substitutions: monomolecular, bimolecular, and borderline mechanisms. The concept of ion pairs. Pericyclic reactions: definition and classification, topology of interactions. Theories of concerted reactions: conservation of orbital symmetry and Woodward and Hoffmann rules, theory of the aromatic transition state, frontier molecular orbitals theory. Reactivity and selectivity. Synthetic applications.