INTRAMOLECULAR REACTIONS OF TEMPORARILY SILICON-TETHERED MOLECULES

The Temporary Silicon Connection transforms a potential intermolecular reaction into an intramolecular one, by transiently connecting both p artners through a silicon linkage. In addition to entropic advantages, temporary connectivity forces regioselectivity and high stereoselecti vity often results. Applications in radical cyclizations, cycloadditio ns, nucleophilic delivery, and hydrosilylation are discussed. Connecti on is also ensured by the coordination of an aldehyde to a Lewis acidi c silicon and has served in aldol and allylation reactions.