|
Lecturer(s)
|
-
Soural Miroslav, doc. RNDr. Ph.D.
|
|
Course content
|
1) Introduction to cross-coupling reactions: historical perspective, catalytic cycle 2) Palladium- or nickel-catalyzed cross-coupling with organometals containing Zn, Mg, Al, and Zi: Systematic survey of palladium- or nickel-catalyzed cross-coupling, assymetric cross-coupling, palladium-catalyzed tandem processes involving cross-coupling reactions, mechanism of cross-coupling 3) Cross-coupling reactions of organoboron compounds with organic halides: Preparation of organoboron compounds, palladium-catalyzed reactions of organoboron compounds and their mechanism, cross-coupling reactions of organoboron compounds 4) Palladium-catalyzed coupling of organyl halides to alkenes - the Heck reaction: Principles, cascade reactions and multiple couplings, related palladium-catalyzed reactions, enantioselective Heck-type reactions 5) Organotin reagents in cross-coupling: Stille coupling of alkenyltins, reactions of substrates where tin is attached to a heterocyclic ring, reactions of aryl- and alkyltins, Reactions involving various types of tetraorganotin, reactions of allyl- allenyl- and propargyltins, related palladium-catalyzed reactions, reactions induced by copper, nickel-catalyzed reactions 6) Cross-coupling reactions to sp carbon atoms: Cross-coupling reactions of alkynylmetal reagents with sp2 carbon atoms, transition-metal-catalyzed cross-coupling 7) Carbometallation reaction: Carbometallation of alkynes, allenes, enynes, alkenes, enantioselective carbometallation of alkenes 8) Palladium-catalyzed 1,4-additions to conjugated dienes: Palladium(O)-catalyzed reactions, palladium(II)-catalyzed reactions 9) Carbon-carbon bond formation reactions mediated by organozinc reagents: Uncatalyzed cross-coupling reactions, copper-catalyzed cross-coupling reactions, Transition-metal-catalyzed cross-coupling reactions 10) Organosilicon compounds in cross-coupling reactions: Coupling reactions of alkenylsilanes, arylsilanes, alkynylsilanes, disilanes, alkylsilanes, allylsilanes, coupling reactions without fluoride ion 11) Palladium-catalyzed coupling reactions of propargylic compounds
|
|
Learning activities and teaching methods
|
|
Work with Text (with Book, Textbook)
|
|
Learning outcomes
|
Carbon-carbon bond forming reactions are arguably the most important processes in chemistry, as they represent key steps in the building of complex molecules from simple precursors. Among these reactions, metal-catalyzed cross-coupling reactions are extensively employed in a wide range of areas of preparative organic chemistry, ranging from the synthesis of complex natural products, to supramolecular chemistry, and materials science. This course is dedicated to overview of all the most frequent types of metall-catalyzed cross-coupling reactions. 1) Introduction to cross-coupling reactions: historical perspective, catalytic cycle 2) Palladium- or nickel-catalyzed cross-coupling with organometals containing Zn, Mg, Al, and Zi: Systematic survey of palladium- or nickel-catalyzed cross-coupling, assymetric cross-coupling, palladium-catalyzed tandem processes involving cross-coupling reactions, mechanism of cross-coupling 3) Cross-coupling reactions of organoboron compounds with organic halides: Preparation of organoboron compounds, palladium-catalyzed reactions of organoboron compounds and their mechanism, cross-coupling reactions of organoboron compounds 4) Palladium-catalyzed coupling of organyl halides to alkenes - the Heck reaction: Principles, cascade reactions and multiple couplings, related palladium-catalyzed reactions, enantioselective Heck-type reactions 5) Organotin reagents in cross-coupling: Stille coupling of alkenyltins, reactions of substrates where tin is attached to a heterocyclic ring, reactions of aryl- and alkyltins, Reactions involving various types of tetraorganotin, reactions of allyl- allenyl- and propargyltins, related palladium-catalyzed reactions, reactions induced by copper, nickel-catalyzed reactions 6) Cross-coupling reactions to sp carbon atoms: Cross-coupling reactions of alkynylmetal reagents with sp2 carbon atoms, transition-metal-catalyzed cross-coupling 7) Carbometallation reaction: Carbometallation of alkynes, allenes, enynes, alkenes, enantioselective carbometallation of alkenes 8) Palladium-catalyzed 1,4-additions to conjugated dienes: Palladium(O)-catalyzed reactions, palladium(II)-catalyzed reactions 9) Carbon-carbon bond formation reactions mediated by organozinc reagents: Uncatalyzed cross-coupling reactions, copper-catalyzed cross-coupling reactions, Transition-metal-catalyzed cross-coupling reactions 10) Organosilicon compounds in cross-coupling reactions: Coupling reactions of alkenylsilanes, arylsilanes, alkynylsilanes, disilanes, alkylsilanes, allylsilanes, coupling reactions without fluoride ion 11) Palladium-catalyzed coupling reactions of propargylic compounds
|
|
Prerequisites
|
Knowledge in the field of organic synthesis.
|
|
Assessment methods and criteria
|
Student performance
Student prepares a clear presentation on a given topic and recites it at a seminar for the research group. For the award of credit is required to prove to adequately respond to questions from the audience and succeeded in the following discussion on a given topic. Students in the advanced stages of study PGS is required presentations and discussions in English.
|
|
Recommended literature
|
-
A. de Meijere, François Diederich. (2004). Metal-Catalyzed Cross-Coupling Reactions. Wiley-VCH.
-
François Diederich, Peter J. Stang. (1998). Metal-Catalyzed Cross-Coupling Reactions. John Wiley and Sons.
-
Norio Myiaura. (2002). Cross-Coupling Reactions A Practical Guide. Springer.
|