93131-36-3Relevant academic research and scientific papers
Cationic rearrangements controlled by the presence of a silyl group
Chénedé, Alain,Fleming, Ian,Salmon, Roger,West, Mark C.
, p. 84 - 93 (2007/10/03)
1,1-Disilylcarbinols having two alkyl groups on the adjacent carbon atom react with thionyl chloride in sulfur dioxide to give the product in which one of the alkyl groups has migrated towards the two silyl groups, and one of the silyl groups has been removed from the resultant cation. The reaction is seen in ring-expansion, as in the conversion of cyclohexylbis[dimethyl(phenyl)silyl]carbinol (7) into 1-dimethyl(phenyl) silylcycloheptene (11), and in open chains, as in the conversion of 1,1-bis[dimethyl(phenyl)silyl]-2-methylpropanol (26) into (E)- and (Z)-2-dimethyl(phenyl)silylbut-2-ene (27). Phenyldimethylsilyllithium reacts with pinacolone to give the α-silyl carbinol (44), which rearranges in the same way to give 2,3-dimethylbut-2-ene (46), effectively achieving a pinacolone-to-pinacol rearrangement.
INTAMOLECULAR CYCLIZATION MEDIATED BY SILYLMETALATION OF ACETYLENES WITH PhMe2SiMgMe/CuI AND RADICAL NATURE OF THE REAGENT
Okuda, Yasuhiro,Morizawa, Yoshitomi,Oshima, Koichiro,Nozaki, Hitosi
, p. 2483 - 2486 (2007/10/02)
Whereas CuI catalyzed silylmagnesation of the tosylate of 5-hexyn-1-ol with the title reagent affords dimethylphenylsilylmethylenecyclopentane exclusively, the mesylate of 3-butyn-1-ol gives a mixture of unexpected silylcyclobutene and cyclopropylidene derivative.
