Radical Brook rearrangement: past, present, and future

Abstract

The Brook rearrangement has emerged as one of the most pivotal transformations in organic chemistry, with broad applications spanning organic synthesis, drug design, and materials science. Since its discovery in the 1950s, the anion-mediated Brook rearrangement has been extensively studied, laying the groundwork for the development of numerous innovative reactions. In contrast, the radical Brook rearrangement has garnered comparatively less attention, primarily due to the challenges associated with the controlled generation of alkoxyl radicals under mild conditions. However, recent advancements in visible-light catalysis and transition-metal catalysis have positioned the radical Brook rearrangement as a promising alternative synthetic strategy in organic synthesis. Despite these developments, significant limitations and challenges remain, warranting further investigation. This review provides an overview of the radical Brook rearrangement, tracing its development from past to present, and offers perspectives on future directions in the field to inspire the creation of novel synthetic tools based on this transformation.