Palladium and Cobalt-Catalyzed Functionalization of sp2 and sp3 Carbon-Hydrogen Bonds

Directed functionalization of C–H bonds has emerged as a practical method for new carbon-carbon and carbon-heteroatom bond formation. Despite the achieved successes, many challenges still remain. First, use of the methodology for functionalization of C–H bonds in phosphorus and sulfur-containing compounds is still rare. Second, functionalization of C–H bonds directed by simple functional groups is limited to second and third-row metal catalysis. This dissertation describes methods for cobalt and palladium-catalyzed, aminoquinoline-directed functionalization of sp2 and sp3 C–H bonds in phosphinic and sulfonic amides. The use of cobalt catalyst for simple carboxylate-directed sp2 C–H functionalization is also reported. Directed functionalization of C–H bonds in aminoquinoline phosphinic acid amides under cobalt catalysis was developed. A simple cobalt salt was used to catalyze the coupling of amide C–H bonds with alkynes, ethylene, and morpholine. To our knowledge, this marks the first example of ortho-functionalization C–H bonds in phosphinic acid derivatives using first row transition metals. Subsequently, beta-arylation of sp3 C–H bonds in alkylphosphinic acid amiquinoline amides with aryl iodides was also described. Furthermore, cobalt-catalyzed, directed carbonylation of C–H bonds in aminoquinoline sulfonamides was developed. Directing group removal affords saccharin derivatives. Finally, carboxylate-directed coupling of sp2 C–H bonds with alkynes, styrenes, and 1,3-dienes under cobalt catalysis was investigated. This reaction is a rare example using simple directing groups for first row metal-catalyzed functionalization of C–H bonds.