Litcius/Paper detail

Silylium-Ion-Promoted Hydrosilylation of Aryl-Substituted Allenes: Interception by Cyclization of the Allyl-Cation Intermediate

Supriya Rej, Hendrik F. T. Klare, Martin Oestreich

2022Organic Letters25 citationsDOI

Abstract

A trityl-cation-initiated, silylium-ion-promoted hydrosilylation of aryl-substituted allenes is reported. Depending on the hydrosilane-to-initiator ratio, the hydrosilylation can be intercepted by an intramolecular electrophilic aromatic substitution or a Nazarov electrocyclization of an allyl-cation intermediate in the form of its endo isomer. By this, the selective formation of either the conventional 1,2-hydrosilylation product (vinylsilane) or a cyclized product (silylated indane) can be controlled.

Topics & Concepts

HydrosilylationChemistryVinylsilaneArylElectrophileIntramolecular forceMedicinal chemistryOrganic chemistryCatalysisAlkylOrganoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization Methods