Methodologies and Strategies for Selective Borylation of C-Het and C-C Bonds.

Organoborons have emerged as versatile building blocks in organic synthesis to achieve molecular diversity and as carboxylic acid bioisosteres with broad applicability in drug discovery. Traditionally, these compounds are prepared by the substitution of Grignard/lithium reagents with electrophilic boron species and Brown hydroboration. Recent developments have provided new routes for the efficient preparation of organoborons by applying reactions using chemical feedstocks with leaving groups. As compared to the previous methods that used organic halides (I, Br, and Cl), the direct borylation of less reactive C-Het and C-C bonds has become highly important to get efficiency and functional-group compatibility. This Review aims to provide a comprehensive overview of this topic, including (1) C-F bond borylation, (2) C-O bond borylation, (3) C-S bond borylation, (4) C-N bond borylation, and (5) C-C bond borylation. Considerable attention is given to the strategies and mechanisms involved. We expect that this Review will inspire chemists to discover more efficient transformations to expand this field.