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

DOI: 10.1039/DT9900001161

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1161 - 1172 (1990)

Update date:2022-08-10

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Authors:

Papasergio, Rocco I.

Skelton, Brian W.

Twiss, Paul

White, Allan H.

Raston, Colin L.

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Article abstract of DOI:10.1039/DT9900001161

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 <(-)sparteine> yields crystalline lithium complexes.These have been characterized using X-ray diffraction data for <2-CH(SiMe3)2C5H4N>> (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 <2.00(1), 1.96(2), 2.19(1), and 1.985(6) Angstroem>, ipso-carbon <2.22(1), 2.43(2), 2.356(9), and 2.323(6) Angstroem>, and adjacent ring carbon <2.32(1), 2.46(2), 2.34(1), and 2.353(6) Angstroem>; in (4) the nitrogen centre also bridges to another metal centre <2.041(1) Angstroem>.Complex (2) has two co-ordinated lithium centres, each lithium bound by the ipso-carbon <2.213(7) Angstroem> and a nitrogen centre from a centrosymmetric ligand <1.936(6) Angstroem> 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-<(1-trimethylsilyl)ethyl>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.

Full text of DOI:10.1039/DT9900001161

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