Catalytic syntheses and copper- or ruthenium-catalyzed direct C H bond arylations of (hetero)arenes

Abstract

The work presented in this thesis represents recent advances in late-transition metal catalyzed cross-coupling reactions and direct arylations. The results described in section 3.1 focus on the development of catalyst systems for Suzuki-Miyaura reactions for the synthesis of sterically hindered biaryls and also for efficient use of challenging 2-pyridyl boronates in this coupling reaction. In addition, the unprecedented general use of 2-pyridyl nucleophiles for Kumada-Corriu cross-coupling reactions are described in section 3.2. The scope of these methods is discussed in depth and the factors that govern the efficacy of the process are elaborated. The aforementioned coupling reactions benefited greatly from the presence of HASPO preligands. Sections 3.4 and 3.4 describe work conducted on the topic of C H bond functionalizations. Mechanistic insight into ruthenium-catalyzed direct arylations are reported in section 3.3. Modular approaches for "sequential" copper-catalyzed synthesis of a wide range of fully substituted triazoles are discussed in section 3.4.