Ir-Catalyzed Borylation of Heterocycles Through C−H Activation

Heteroaromatic compounds play a crucial role in the fields of pharmaceuticals and materials science, providing a range of functionalities that are essential for a wide array of applications. The exploration of iridium-catalyzed C-H borylation in heteroarenes stands as a significant advancement in synthetic organic chemistry, delving into issues of regioselectivity and intricate mechanisms. Unlike carbocyclic arenes, where steric considerations predominantly govern selectivity, heteroarenes demonstrate a higher degree of intrinsic electronic regiocontrol. Overcoming challenges associated with heteroarenes, including the complex interplay of electronic and steric factors, numerous studies have investigated systematic diversification based on intriguing mechanistic aspects. Catalyst engineering, involving unique ligand design, and substrate modification strategies have been explored. In this book chapter, we have dedicated our endeavors to uphold the inception and conceptual analysis of various facets of C−H borylation in heteroarenes, highlighting the influence of electronic and steric effects, directed borylation, and the emerging paradigm of non-covalent interactions. The discussion connects these aspects to current mechanistic understandings and proposes avenues for further development.