Industrial Chemistry

LUISA MARIA MIGNECO
LUISA MARIA MIGNECO

Organic Synthesis is an advanced branch of knowledge in the field of Organic Chemistry, that allows to build the molecular frame of complex targets not randomly but in a focused and efficient way. Organic Synthesis represents also an area of industrial expertise, as most of synthetic targets are bioactive molecules of high added value, and sustainability in their preparation process is an up-to-date challenge.
General educational objectives of the course are: to confer knowledge of the main strategies and methodologies in organic synthesis, and to improve knowledge in preparative organic chemistry processes’ set up by lectures and class practice. As expected results of the learning path, students will be able to project the synthesis of a simple organic compound by means of logic principles, to know how to realize a modern synthesis by the Green Chemistry approach and also to describe simple organic preparative procedures.
At the end of the course (specific objectives) students will be able to: have a wider knowledge of organic chemistry and especially organic synthesis, also by way of the rational approach to modern organic synthesis, i.e. the logic of organic synthesis (lectures); to devise synthetic routes to simple organic molecules as targets, and to have a basic knowledge in the field of green synthesis (lectures); to expand their knowledge in preparative organic chemistry (lectures and class practice). They will also be able, by applying cross knowledge in organic reactions, to evaluate the best synthetic path among many (examples in lectures and class practice) and to discuss synthetic plans with the correct scientific language (questions and examples in lectures and class practice). The in-depth knowledge of organic reactions topics will give students the ability to continue studying organic chemistry on their own.

To acquire knowledge of the main strategies and methodologies in organic synthesis, and to improve knowledge in preparative organic chemistry processes’ set up by lectures and class practice.

Required knowledge: periodic table structure, electronic configuration and electronegativity of elements; main types of chemical bonds, ibridation, resonance structures; Broensted and Lewis acids and bases; organic functional groups, polarity, basic and acid behaviour, electrophilicity and nucleophilicity; organic functional classes, IUPAC nomenclature, physico-chemical features and reactivity; main types of organic reactions (additions, substitution, etc.) and their mechanisms; organic synthetic reactions; stereochemistry basics (enantiomers amd diastereoisomers, racemic mixtures, Cahn-Ingold-Prelog rules)

ORGANIC SYNTHESIS PRINCIPLES

Preparative organic reactions, their features and distinctive parameters. Theorical and percentage yield. Experimental parameters of organic reactions: reaction medium, temperature, pressure, stirring. Solubility-structure relationship. Organic solvents: protic and aprotic solvents, dielectric constant; density, water solubility, boiling point. Purification and manipulation of organic solvents.

What is organic synthesis? Definition and scope of organic synthesis. Total and partial synthesis, linear and convergent synthesis, formal total synthesis, definitions and some examples.
The history of organic synthesis, from Woelher’s urea to nowadays. Important examples in the history of organic synthesis. Contemporary organic synthesis and its features. The rational approach to organic synthesis: the logic of chemical synthesis.
How can we project a synthesis? Strategy and tactics. Synthons and synthetic equivalents. The disconnection approach. Retrosynthetic analysis, target molecule. Functional group interconvertions (FGI) and functional group addition (FGA). Use of activating and protective groups in organic synthesis. Some important types of disconnections of one and two groups; examples and discussion.
Criteria for a stereoselective synthesis. Definition of prochiral systems, examples. Asymmetric induction, use of chiral solvents, chiral auxiliaries, chiral catalysts. Organocatalysis, definition and applications. Enantiosynthesis, use of chiral building blocks, the chiral pool approach.
Criteria for a modern synthesis: selectivity and efficiency; atom and step economy.
Discussion on the synthesis of some complex bioactive compounds.

GREEN CHEMISTRY: APPLICATION TO ORGANIC SYNTHESIS
What is Green Chemistry? The twelve topics of green chemistry. Green chemistry and organic synthesis.
Criteria for a compatible synthesis. Use of eco-friendly, non toxic, reagents and materials; use of compatible solvents, catalytic reaction conditions. Eco-compatible solvents: supercritical fluids, description and features, supercritical CO2, examples of industrial application; ionic liquids, description, chemical features and application to organic reactions; glycerol as a solvent in organic synthesis; water as a solvent, scope, application and limitations. Catalysts and their use in green organic synthesis: heterogeneous and homogeneous catalysts, their features and drawbacks. Use of renewable feedstocks: biomass and its use as a source of chiral building blocks in organic synthesis.

CLASS PRACTICE related to the main topics of the course (C-C bond forming reactions and functional groups interconversions; synthetic strategy; examples of published synthesis); focus and discussion on preparative organic procedures.

Lecture notes and handouts available from the beginning of the course.
A good textbook of basic organic chemistry.

The course is articulated in 56 h of lectures and 24 h of class practice. Class will be based on slides illustrating the contents of each lesson. A copy of the slides is available at the beginning of the course, together with the detailed programme.
Lessons follow a weekly articulation which is approved in advance by the Industrial Chemistry "Consiglio di Area Didattica" (CAD).

optional, recommended

The oral exam will allow to evaluate how knowledge and understanding of the logic of chemical synthesis have been developed; how the fundamentals of Green Chemistry protocol have been understood and can be applied to simple organic procedures; how set-up features of organic preparative procedures have been critically understood. The oral exam will also allow to evaluate if reasoning and critical thinking in the field of organic synthesis have been developed, and if communication skills fit the educational level of Laurea Magistrale.

Willstaetter and Robinson syntheses of tropinone, total synthesis of swainsonine; asymmetric induction; C-C bond forming reactions