Palladium catalyzed C–H functionalization of amine derivatives and its application in total synthesis

The aim of this thesis was to develop novel and efficient methodologies to functionalize amine containing compounds. We have adopted different tactics to functionalize different amine substrates. In Chapter 2, the combination of a monodentate directing group, triflyl protected amine, with pyridine- or quinoline-based external ligand to promote Pd-catalyzed γ-C(sp³)–H acetoxylation of aliphatic amines is described. Chapter 3 describes the non-directed highly para-selective olefination reaction of indolines and tetrahydroquinolines by using Pd/S,O-ligand catalysis under mild reaction conditions. This transformation shows broad substrate scope regarding indolines, tetrahydroquinolines and olefins. This chapter also contains examples for late-stage selective functionalization of complex molecules. In Chapter 4, the methodology described in Chapter 3 is applied for the divergent total synthesis of yaequinolone related natural products. To achieve this goal, a reliable synthetic sequence for the preparation of 3,4-dioxygenated 5-hydroxy-4-aryl-quinolin-2(1H)-ones, which are the core structures of this family of natural products, is described. Then, by performing para-selective late-stage olefination on these core structures, we successfully realized the total synthesis of 11 yaequinolone related natural products.