| Literature DB >> 25879515 |
Allegra L Liberman-Martin1,2, Robert G Bergman1,2, T Don Tilley1,2.
Abstract
Bis(perfluorocatecholato)silane Si(cat(F))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(cat(F))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 NBu4BAr(F)4 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.Entities:
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Year: 2015 PMID： 25879515 PMCID： PMC4428610 DOI： 10.1021/jacs.5b02807
Source DB: PubMed Journal: J Am Chem Soc ISSN： 0002-7863 Impact factor: 15.419