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Over the past two decades, the C–H bond activation and functionalization reaction has been known as a prevailing method for the construction of carbon–carbon and carbon–heteroatom bonds using various transition metal catalysts. In this context, the iridium-catalyzed C–H bond activation and borylation reaction is one of the most valued methods. However, the major challenge in these borylation reactions is how to control the proximal (ortho) and distal (meta and para) selectivity. Interestingly, while so many approaches are now available for the proximal ortho selective borylation of arenes, borylation at the distal meta and or para position of arenes remains still challenging. Only a few approaches have been reported so far in the literature employing iridium catalysis. In this feature article, we have demonstrated some of the recent discoveries from our laboratories for the proximal (ortho) and distal (meta and para) selective borylation reactions. Moreover, some of the recent catalyst engineering discoveries for the selective proximal ortho borylation reactions for a diverse class of substrates have also been discussed. The discussion part of several other pioneering reports is limited due to the lack of scope of this feature article. [ABSTRACT FROM AUTHOR]

Transition metal-catalysed direct borylation of hydrocarbons via C–H bond activation has received a remarkable level of attention as a popular reaction in the synthesis of organoboron compounds owing to their synthetic versatility. While controlling the site-selectivity was one of the most challenging issues in these C–H borylation reactions, enormous efforts of several research groups proved instrumental in dealing with selectivity issues that presently reached an impressive level for both proximal and distal C–H bond borylation reactions. For example, in the case of ortho C–H bond borylation reactions, innovative methodologies have been developed either by the modification of the directing groups attached with the substrates or by creating new catalytic systems via the design of new ligand frameworks. Whereas meta and para selective C–H borylations remained a formidable challenge, numerous innovative concepts have been developed within a very short period of time by the development of new catalytic systems with the employment of various noncovalent interactions. Moreover, significant advancements have occurred for aliphatic C(sp3)–H borylations as well as enantioselective borylations. In this review article, we aim to discuss and summarize the different approaches and findings related to the development of directed proximal ortho, distal meta/para, aliphatic (racemic and enantioselective) borylation reactions since 2014. Additionally, considering the C–H borylation reaction as one of the most important mainstream reactions, various applications of this C–H borylation reaction toward the synthesis of natural products, therapeutics, and applications in materials chemistry will be summarized in the last part of this review article. [ABSTRACT FROM AUTHOR]