129548-86-3Relevant articles and documents
Lithiation of 2-Me3SiCHRC5H4N (R = H or SiMe3): Influence of Solvent on the Nature of the Product (from X-Ray Structure Determinations) and Asymmetric Induction. A Note on the Lithiation of Some Analogous 3- and 4-Methylpyridines
Papasergio, Rocco I.,Skelton, Brian W.,Twiss, Paul,White, Allan H.,Raston, Colin L.
, p. 1161 - 1172 (1990)
Metallation of 2-Me3SiCHRC5H4N (R = H or SiMe3) using LiBun in hexane, and in the presence of diethyl ether, and the ditertiary amines tmen (N,N,N',N'-tetramethylethylenediamine) or sp yields crystalline lithium complexes.These have been characterized using X-ray diffraction data for > (1), >2> (2), > (3), >2> (4), >2> (5), and > (6).In (1), (3), (4), and (6) the hydrocarbyl group acts as an η3-aza-allyl through the ring nitrogen , ipso-carbon , and adjacent ring carbon ; in (4) the nitrogen centre also bridges to another metal centre .Complex (2) has two co-ordinated lithium centres, each lithium bound by the ipso-carbon and a nitrogen centre from a centrosymmetric ligand and is thus an alkylmetal species; it can be recrystallized from tetrahydrofuran even though the lithiums are co-ordinatively unsaturated.In complex (5), the anionic ligand acts as an amide bridging two metal centres through the ring N .Treating (6) with MeI in hexane at -78 deg C yields 2-pyridine of 20percent estimated optical purity.The isomeric complex > under the same conditions gave no asymmetric induction; other metallations of 4-Me3SiCH2C5H4N, and some of 3-Me3SiCH2C5H4N are also reported.
