1354637-00-5Relevant articles and documents
Lewis acidity of bis(perfluorocatecholato)silane: Aldehyde hydrosilylation catalyzed by a neutral silicon compound
Liberman-Martin, Allegra L.,Bergman, Robert G.,Tilley, T. Don
, p. 5328 - 5331 (2015)
Bis(perfluorocatecholato)silane Si(catF)2 was prepared, and stoichiometric binding to Lewis bases was demonstrated with fluoride, triethylphosphine oxide, and N,N′-diisopropylbenzamide. The potent Lewis acidity of Si(catF)2 was suggested from catalytic hydrosilylation and silylcyanation reactions with aldehydes. Mechanistic studies of hydrosilylation using an optically active silane substrate, R-(+)-methyl-(1-naphthyl)phenylsilane, proceeded with predominant stereochemical retention at silicon, consistent with a carbonyl activation pathway. The enantiospecificity was dependent on solvent and salt effects, with increasing solvent polarity or addition of NBu4BArF4 leading to a diminished enantiomeric ratio. The medium effects are consistent with an ionic mechanism, wherein hydride transfer occurs prior to silicon-oxygen bond formation.
