Palladium-Catalyzed C H Functionalization, Studies Toward Ginkgolide C

The field of metal-catalyzed C H bond functionalizations is an incredibly vibrant and spans beyond the formations of biaryl motifs. The mechanistic aspects of the C H bond functionalization with metal-carboxylate complexes are highlighted. The role of additives, such as pivalic acid, is demonstrated with poorly reactive substrates. A chapter describes experimental and computational studies which suggested that a single pathway might be involved in the palladium-catalyzed C H bond functionalization of a wide range of (hetero)arenes. Afterward a general set of conditions are developed to form biaryls by direct arylation with a wide range of heteroarenes of various complexity level. The development of two new Pd-catalyzed methods based on our knowledge on the C H bond cleavage are apply to the formation of new scaffolds. Efforts toward the development of ligands to specifically promoted C H bond cleavage are presented. Lastly, most recent results on the study of the mechanism of the C H bond cleavage combining experimental and computational studies are discussed. In the second part of the thesis are presented our strategy toward the synthesis of ginkgolide C using gold catalysis.

Autorentext

David was born and raised in the countryside of a little town located in the eastern townships in Québec, Canada. He obtained his B.S. in chemistry from the Université de Sherbrooke, then moved to Ottawa, to pursue his doctoral studies at the University of Ottawa, in the group of the late Prof. Keith Fagnou and in the group of Prof. Louis Barriault

Klappentext

The field of metal-catalyzed C H bond functionalizations is an incredibly vibrant and spans beyond the formations of biaryl motifs. The mechanistic aspects of the C H bond functionalization with metal-carboxylate complexes are highlighted. The role of additives, such as pivalic acid, is demonstrated with poorly reactive substrates. A chapter describes experimental and computational studies which suggested that a single pathway might be involved in the palladium-catalyzed C H bond functionalization of a wide range of (hetero)arenes. Afterward a general set of conditions are developed to form biaryls by direct arylation with a wide range of heteroarenes of various complexity level. The development of two new Pd-catalyzed methods based on our knowledge on the C H bond cleavage are apply to the formation of new scaffolds. Efforts toward the development of ligands to specifically promoted C H bond cleavage are presented. Lastly, most recent results on the study of the mechanism of the C H bond cleavage combining experimental and computational studies are discussed. In the second part of the thesis are presented our strategy toward the synthesis of ginkgolide C using gold catalysis.