Radical‐Mediated 1,2‐Boryl Migration: An Emerging Strategy Toward Diverse Boronate Molecules and Polymers

ABSTRACT Organoboronates represent indispensable synthetic handles and functional building blocks, motivating the continuous development of innovative strategies for their construction and structural editing. In recent years, the radical‐mediated 1,2‐boryl migration strategy, enabled by the unique electronic characteristics of the boron center, has transcended the constraints of ionic manifolds and flourished as a powerful tool for molecular editing. Merging this rearrangement with state‐of‐the‐art systems, such as photoredox catalysis, energy‐transfer activation, hydrogen atom transfer, and polarity‐matching approaches, has not only enabled the efficient synthesis and transposition editing of diverse small‐molecule organoboronates but has also recently expanded its frontiers into polymer synthesis. This perspective aims to provide an overview of recent advances in radical‐mediated 1,2‐boryl migration strategies spanning both small‐molecule and polymer synthesis, offering insights into the design of novel radical rearrangements and their applications in precision materials fabrication.