38711-74-9Relevant academic research and scientific papers
Studies on the reactive species in fluoride-mediated carbon-carbon bond-forming reactions: Carbanion formation by desilylation with fluoride and enolates
Biddle, Margaret M.,Reich, Hans J.
, p. 4031 - 4039 (2006)
The reactive species in fluoride-mediated carbon-carbon bond-forming reactions was investigated. The regio- and diastereoselectivities of silanes reacting with cyclohexenone in the presence of a catalytic amount of fluoride was compared to the reactivity of analogous solvent-separated lithium ion pairs. Closely analogous behavior was observed, showing that carbanions and not siliconate complexes are the reactive species in the fluoride-catalyzed reactions. Spectroscopic investigations unambiguously show that phenylthiobenzyl anion will form by reaction of silane with tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF) or crypt[2.1.1]-solvated lithium enolates. The catalytic cycle runs smoothly with the crypt[2.1.1] complex of α-(phenylthio)benzyllithium as the initiator and enolate as the carrier of the desilylation reaction.
