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Updated: May 22, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Base-free dehydrogenative coupling of enolizable carbonyl compounds with silanes
C David F Königs1, Hendrik F T Klare, Yasuhiro Ohki
1Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany.
Abstract:
A dehydrogenative coupling between enolizable carbonyl compounds and equimolar amounts of triorganosilanes catalyzed by a tethered ruthenium complex with a Ru-S bond is reported. The complex is assumed to fulfill a dual role by activating the Si-H bond to release a silicon electrophile and by abstracting an α-proton from the intermediate silylcarboxonium ion, only liberating dihydrogen as the sole byproduct. Reaction rates are exceedingly high at room temperature with very low loadings of the ruthenium catalyst.
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