Silylium-Ion-Promoted Hydrosilylation of Aryl-Substituted Allenes: Interception by Cyclization of the Allyl-Cation Intermediate.
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DOI: 10.1021/acs.orglett.2c00011
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… read more here.
Keywords: hydrosilylation; silylium ion; hydrosilylation aryl; cation ... See more keywords
Ga+-catalyzed hydrosilylation? About the surprising system Ga+/HSiR3/olefin, proof of oxidation with subvalent Ga+ and silylium catalysis with perfluoroalkoxyaluminate anions
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DOI: 10.1039/d1sc05331k
Abstract: Already 1 mol% of subvalent [Ga(PhF)2]+[pf]− ([pf]− = [Al(ORF)4]−, RF = C(CF3)3) initiates the hydrosilylation of olefinic double bonds under mild conditions. Reactions with HSiMe3 and HSiEt3 as substrates efficiently yield anti-Markovnikov and anti-addition products,… read more here.
Keywords: subvalent; hydrosilylation; catalysis; silylium ion ... See more keywords