| This thesis concerns the development and application of novel synthetic methods based on C-H bond activation to a diverse array of synthetic problems. First, a terpene core of a protein kinase C activator, Teleocidin B-4, was constructed in a diastereoselective fashion from a simple tert-butyl aniline building block by an efficient four-step process involving a double palladium-mediated C-H bond functionalization of unactivated alkane fragments. Second, a new catalytic system for the direct arylation of C-H bonds in electron-deficient azines was discovered. This ruthenium-catalyzed coupling is complementary to the existing methods for arylation of electron-rich azoles and expands the synthetic toolbox available for the systematic diversification of nitrogen-containing heteroarenes. Finally, borylation of aromatic C-H bonds has been explored in the context of functionalization of the contorted form of hexabenzocoronene, an interesting scaffold for molecular electronics. A general method for the functionalization of this substrate---consisting of an iridium-catalyzed C-H bond borylation and a palladium-catalyzed cross-coupling of the resulting hexabenzocoronene boronates with iodoarenes---was devised, providing access to a number of new synthetic materials with potentially interesting physical and electronic properties. |
