Carbon-hydrogen bond functionalization of arenes using transition metal catalysis has experienced a renaissance in recent decade. This powerful approach offers the most straightforward way to build up molecular complexity and streamline the synthesis of otherwise difficult to access organic compounds. In this dissertation, general methods for rapid introduction of fluorinated substituents via copper catalysis have been developed. A broadly applicable method for deprotonative, copper-catalyzed C-H arylation of 1H-perfluoroalkanes with aryl iodides was developed. Unparalleled reaction scope with respect to aryl iodides and fluorinated counterparts allows rapid access to multitude of structurally related molecules. Additionally, a method for the direct introduction of trifluoromethylsulfenyl group onto aromatic ring via removable auxiliary directed, copper-catalyzed C-H bond activation of carboxylic acid derivatives was developed.
Finally, copper-promoted palladium-catalyzed C-H arylation of polyfluoroarenes bearing sensitive functional groups with aryl iodides was applied to the synthesis of precursors for the supramolecular assemblies and functional materials such as HOFs and MOFs. These materials are anticipated to have unique adsorption and binding properties.