Part I. Approaches toward the total synthesis of tyloindicine F. Part II. Palladium-catalyzed carbon-hydrogen functionalization of beta-enaminones

Tyloindicine F is a potent anticancer natural product first isolated from the Himalaya region of India. It demonstrated a unique profile in the NCI60 human tumor cell line anticancer drug screen. Due to its scarcity from natural sources, a total synthesis of tyloindicine F is desirable. Two attempts at the synthesis of this natural product have been conducted and are discussed. beta-Enaminones are a group of push-pull olefins whereas C--H functionalization/C--C coupling is a highly efficient method of constructing new carbon-carbon bonds.beta-Enaminones are highly polarized and their a position is suitable for C--H functionalization by means of electropalladation. A novel methodology for the oxidative Hiyama coupling of beta-enaminones has been developed and two new bifunctional activators/reoxidants have been found. Furthermore, a non-oxidative version for beta-enaminone C--H functionalization and the decarboxylative coupling of beta-enaminones were also investigated.