Anorganische Chemie, Technische Universität Dortmund, Otto-Hahn-Straße 6, 44263 Dortmund, Germany.
Dalton Trans. 2012 Mar 28;41(12):3452-60. doi: 10.1039/c2dt12163h. Epub 2012 Feb 3.
The preparation of aminomethyl functionalised silanes based on the α-lithiated amine, (1R,2R)-N,N,N',N'-tetramethylcyclohexane-1,2-diamine [(R,R)-TMCDA] is reported. This methodology can be applied for the synthesis of mono-aminomethyl substituted systems, but most remarkably also for di- and trifunctionalised compounds. The trapping of the lithiated amine is accompanied by transmetallation reactions resulting in the formation of (silylmethyl)silanes depending on the reaction temperature. The zinc(II) halide complexes of the mono-functionalised systems show the formation of exclusively one configuration of the stereogenic nitrogen atom, in which the spatially more demanding substituent exhibits the pseudo-equatorial position. The di- and trifunctionalised systems feature high sensitivity towards Si-C bond cleavage under re-formation of the (R,R)-TMCDA fragment.
本文报道了基于 α-锂化胺（1R,2R）-N,N,N',N'-四甲基环己烷-1,2-二胺[(R,R)-TMCDA]的氨甲基功能化硅烷的制备。该方法可用于合成单氨甲基取代体系，但最显著的是还可用于二和三官能化化合物。锂化胺的捕获伴随着转金属反应，根据反应温度形成（甲硅烷基）硅烷。单官能化体系的锌（II）卤化物配合物表现出形成立体氮原子的唯一构型，其中空间要求较高的取代基呈现假赤道位置。二和三官能化体系对 Si-C 键的重新形成具有高灵敏度，导致（R,R）-TMCDA 片段的重新形成。
