COOPERATIVITY IN CATALYSIS: CO-CATALYST ASSISTED PALLADIUM-CATALYZED TRANSFORMATIONS

Abstract

This thesis describes our efforts in the development of novel co-catalyst assisted palladium-catalyzed transformations for the synthesis of valuable organic molecules. Drawing inspiration from a structurally interesting, bis-coordinating pyridazine ligand we synthesized, three separate discoveries were made. The first discovery involves an unprecedented copper(I) iodide assisted palladium-catalyzed trimerization of terminal alkynes. This reaction provides an operationally simple procedure to access acyclic Z-enediynes - a class of compound with proven anti-cancer properties. The second discovery involves a chiral amine assisted palladium-catalyzed α-allylation of unfunctionalized ketones. The enantioselective protocol described herein provides a direct method for the synthesis of valuable α-tertiary stereogenic centres. The thesis also describes the extensive screening of reaction parameters we undertook to realize this challenging organic transformation. Lastly, we present our preliminary findings on an f-block co-catalyst assisted palladium-catalyzed amination of primary alcohols via Borrowing-Hydrogen methodology.