34041-44-6Relevant articles and documents
Reductive lithiation of alkyl phenyl sulfides in diethyl ether. A ready access to α,α-dialkylbenzyllithiums
Screttas, Constantinos G.,Heropoulos, Georgios A.,Micha-Screttas, Maria,Steele, Barry R.,Catsoulacos, Dimitrios P.
, p. 5633 - 5635 (2007/10/03)
Diethyl ether is a convenient solvent for the conversion of benzylic phenyl sulfides to the corresponding organolithiums by an uncatalyzed reductive metalation, while catalysis by naphthalene is required to achieve the same reaction for alkyl phenyl sulfides. The addition of magnesium 2-ethoxyethoxide to solutions of unstable alkyllithiums prepared in this way provides storable reagents.
Reaction of Phenyl-Substituted Allyllithiums with tert-Alkyl Bromides. Remarkable Difference in the Alkylation Regiochemistry between a Polar Process and the One Involving Single-Electron Transfer
Tanaka, Jiro,Nojima, Masatomo,Kusabayashi, Shigekazu
, p. 3391 - 3397 (2007/10/02)
The reaction of phenyl-substituted allyllithiums 1a-h with tert-alkyl bromides was investigated systematically.The alkylation regiochemistry was influenced in a complicated fashion by various factors including substituent effects, both steric and electronic, solvents, and the presence of strongly coordinating additives, tetramethylethylenediamine and hexamethylphosphoramide.On the basis of the cyclizable probe experiments, the observed regiochemistry was interpreted as follows. (a) The reaction proceeds by two alternative pathways, a polar one and single electron transfer (SET), the extent of each path being influenced by the variable factors and (b) a polar pathway favors coupling at the phenyl-substituted site (C-1), while in the case of SET the C-C bond formation occurs predominantly at the site far from the phenyl substituent (C-3).