The Brook Rearrangement

Abstract

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.

Radical Brook Rearrangements: Concept and Recent Developments

“…Interestingly, the products could be transformed into thiolated 1,4-diketones and complex architectures containing seven-membered rings. Acylsilane undergoes a Brook rearrangement through a concerted-type silyl migration [56] to produce a siloxycarbene species under thermal or photochemical conditions, which has recently been employed by the groups of Glorius, [57] Studer, [58] Toste and Nomura, [59] Shen, [60] and Kusama [61] using visible light conditions. Related photocatalytic reactions based on this type of migration have been reviewed very recently, however, and will not be discussed in detail here.…”

Unveiling Novel Synthetic Pathways through Brook Rearrangement

“…First discovered by Gilman 1 and subsequently recognized by Brook, 2 this rearrangement has since attracted considerable attention, both regarding the mechanism and its implication in synthetic organic chemistry. 3 4 5 6 7…”

Bimetallic tandem catalysis-enabled enantioselective cycloisomerization/carbonyl–ene reaction for construction of 5-oxazoylmethyl α-silyl alcohol

“…As a special subset, chiral tertiary α-silyl alcohols serve as important building blocks in versatile transformations for the construction of complex molecules. 3 Asymmetric nucleophilic addition to acylsilanes 4 containing an sp 2 carbon atom binding to both a silicon and an oxygen atom is one of the most direct and efficient accesses to optically active α-silyl alcohols ( Scheme 1a ), 4 and has attracted considerable attention in the past two decades. A series of intriguing studies were realized by several groups, wherein highly active nucleophilic reagents, such as organometallic reagents, 5 a – e , h enamine, 5 f enolate, 5 g or thiol, 5 i were commonly employed to offset the poor reactivity of the acylsilanes.…”