Intramolecular Reactions of Temporarily Silicon-Tethered Molecules

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Abstract
The Temporary Silicon Connection transforms a potential intermolecular reaction into an intramolecular one, by transiently connecting both partners through a silicon linkage. In addition to entropic advantages, temporary connectivity forces regioselectivity and high stereoselectivity often results. Applications in radical cyclizations, cycloadditions, nucleophilic delivery, and hydrosilylation are discussed. Connection is also ensured by the coordination of an aldehyde to a Lewis acidic silicon and has served in aldol and allylation reactions.

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