The Brook Rearrangement

The Brook rearrangement describes the intramolecular silyl group migration from a carbon to an oxygen atom in a “through‐space” fashion. This feature has been extensively applied to develop numerous useful transformations of diverse organosilanes. Some representative examples include formal [3 + 2] and [4 + 3] annulations to construct diverse ring systems, syntheses of configurationally defined silyl enol ethers, multi‐component reactions by Brook rearrangement‐based ARC (anion relay chemistry), and various umpolung processes such as silyl benzoin condensations and sila‐Stetter reactions. This chapter presents a thorough overview of the Brook rearrangement. The scope and limitations are categorized according to the organosilane type. The mechanism and stereochemical course of this process are discussed, as is its application in the synthesis of complex natural products. The literature is covered up to the end of 2019.