Silicon‐Derived Singlet Nucleophilic Carbene Reagents in Organic Synthesis

Over fifty years ago, the 1,2-rearrangement of acylsilanes was first described by Adrian Brook and co-workers. This rearrangement (now termed the Brook rearrangement) yields reactive silicon-based singlet nucleophilic carbene (SNC) intermediates that participate in a variety of chemical transformations including 1,2-carbonyl addition, 1,4-addition to electron-deficient unsaturated bonds and insertion into C−H and O−H bonds. This review aims to cover the historical literature and recent advances with regard to these valuable silicon-based reagents and highlight additional aspects related to the intriguing reactivity of both the carbene and oxocarbenium intermediates.