66290 - Catalysis in Organic Synthesis

Learning outcomes

At the end of the course, the student is able to interpret, understand and design new catalytic reactions, through the understanding of the coordination geometries of complexes, properties of binders, and catalytic cycles, in stereoselective and non-stereoselective reactions. The student also gains experience on some of the most modern experimental procedures in the field of asymmetric synthesis (catalysis) and in the instrumental resolution of stereoisomeric mixtures of organic compounds.

Course contents

Chapter 1. Introduction to the Mayr scale. The Scala di Mayr. Electrophiles and nucleophiles. Definition and use of the relation of the velocity k. Examples and discussion.

Chapter 2. Milestones in industrial catalysis and notes on industrial catalysis. brief discussion on catalytic cycles Rate determinig step, and problems in the definition of TOF and TON. Aspects of a catalytic cycle.

Chapter 3. Organocatalysis. Introduction and ways of activation. Main organocatalysts and use of Mayr scale concepts for the main organocatalytic reactions. Examples of catalysis via enamine and iminium. Multicomponent organocatalytic reactions (outline). Cinchona alkaloids in organocatalysis. Catalysis via carbeni. Nucleophilic catalysis. Catalysis from Bronsted acids. Thiourea. Catalysis ACDC. Phase transfer catalysis. Catalysis SOMO. Photoredox catalysis, introduction, key concepts and application to organocatalytic reactions.

Chapter 4. Phosphine properties and important parameters. Phosphine classes. employed. Hydrogenation reactions and mechanism. Chiral phosphines, their use and properties. Hydrogenation of non-functionalized alkenes. Hydrogenation of ketones, imines. Transfer hydrogenation reactions. Use of iron and cobalt in hydrogenations.

Chapter 5. Introduction to heterogeneous catalysis. Methodologies, scope and development. (Chapter to read)

Chapter 6. Cross coupling reactions (palladium and nickel). Palladium salts. Sources of palladium (0). Pd (I), Pd (II) or Pd (III). Oxidative addition and reductive elimination. Various key points of the catalytic cycle Differences of reactivity such as binders and methodologies. Main classes of reactions (examples). Catalysis with Nickel. Photoredox catalysis with nickel. Buckwald-Hartwig reactions. Mechanism of reactions and binders. Hartwig's phosphines and Buchwald's phosphines. Historical development of the reaction. modern variants. Examples of application of cross coupling reactions in the industrial sector.

Chapter 7. Modern DFT methods and study of catalytic systems with Palladio (outline)

Chapter 8. Cross coupling reactions with copper (Buchwald-Hartwig and Chan-Lam-Evans)

Chapter 9. Cross coupling with cobalt and iron. Applications

Chapter 10. C-H activation, direct arylations, and cross coupling. Palladium, Ruthenium and Iridium in C-H activation reactions. Activation with cobalt, manganese and iron metals. Buchwald-Hartiwg with CH activation.

Cpapter 11. Metathesis reactions

Laboratory course

Advanced laboratory techniques relating to aspects of asymmetric catalysis. Synthesis of hetero-aromatic polycyclic systems in enantiomerically enriched form through the use of gold-based chiral transition metal complexes. Synthesis of chiral building blocks for anti-inflammatory preparation, through the use of chiral organ-catalysts. Use of inert gas lines. 

Readings/Bibliography

PDF notes of the course (teacher's notes) available on UNIBO educational material. Articles provided by the teacher.

Teaching methods

Frontal course with transparencies projected in class and commented with the help of interactive screens or blackboard..

Assessment methods

Written exam with five theory questions (one laboratory question) and two exercises on catalytic cycles (conditions, retrosynthesis, use) on the course material.

Score 5 points (starting score) + 20 points (exam) + 10 points (laboratory). Score for honoring 33 points.

10 laboratory points are divided into 4 points for laboratory behavior and attitude and 6 points for laboratory course questions.

The 20 points of the exam are divided into 4 questions (at the discretion of the teacher 4 x 2 points) and 1 laboratory (6 points), and two exercises of catalytic methodologies (2 x 3 points)

Teaching tools

Course lecture notes made available by the teacher. Slides of the course made available by the teacher.

Office hours

See the website of Pier Giorgio Cozzi

See the website of Marco Bandini