Novel c–h functionalization reactions assisted by 2-pyridyl-containing directing groups

Résumé

The catalytic functionalization of unreactive CH bonds is an area of growing importance for the design of atom economical strategies to valuable organic molecules. However, due to the ubiquity of CH bonds in organic molecules, achieving perfect site-selectivity and high functional group tolerance has been one of the major challenges in this area. In this context, this dissertation outlines our efforts to develop key structure building CH functionalization reactions that streamline the construction of complex molecular skeletons based on the use of 2-pyridyl-containing directing groups. In particular, we have achieved: - The construction of CN bonds through a Cu-catalyzed cross-dehydrogenative coupling strategy. - The development of a Rh-catalyzed tandem process that involves the formation of CC and CX bonds. - A switchable site-selectivity through catalyst control in the direct Rh-catalyzed functionalization of molecules that contain distinct CH bonds. - A catalyst-controlled selectivity in the Rh-catalyzed C(sp2)–H functionalization with 1,3-diynes involving cyclization cascade processes. - The Co-catalyzed alkyne annulation of N-containing arenes through CH/NH functionalization.