Synthetic and Methodological Studies in Copper and Palladium–Catalyzed Carbon-Carbon and Carbon-Heteroatom Bond Formation



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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.



Copper catalysis, Carbon-hydrogen bond activation, Metal-organic frameworks


Portions of this document appear in: Popov, Ilya, Sergey Lindeman, and Olafs Daugulis. "Copper-Catalyzed Arylation of 1 H-Perfluoroalkanes." Journal of the American Chemical Society 133, no. 24 (2011): 9286-9289. And in: Tran, Ly Dieu, Ilya Popov, and Olafs Daugulis. "Copper-promoted sulfenylation of sp2 C–H bonds." Journal of the American Chemical Society 134, no. 44 (2012): 18237-18240. And in: Popov, Ilya, Hien-Quang Do, and Olafs Daugulis. "In situ generation and trapping of aryllithium and arylpotassium species by halogen, sulfur, and carbon electrophiles." The Journal of organic chemistry 74, no. 21 (2009): 8309-8313. And in: Chen, Teng-Hao, Ilya Popov, Oussama Zenasni, Olafs Daugulis, and Ognjen Š. Miljanić. "Superhydrophobic perfluorinated metal–organic frameworks." Chemical Communications 49, no. 61 (2013): 6846-6848.