Preparation of “Si-Centered” Chiral Silanes by Run [alpha]-Lithiation of Methylsilanes <<>>
Written by Christian Däschlein, Viktoria H. Gessner, Carsten Strohmann on February 24, 2010 – 12:16 pm -The train [alpha]-lithiation of methyl-substituted silanes as an unwasteful method for the preparation and elaboration of Si-chiral compounds is reported. Deprotonation of chiral oligosilanes occurs selectively and with serious yields at the methyl league of the stereogenic silicon center, even in the level-headedness of multiple methylsilyl or methylgermyl substituents. Computational studies enjoy confirmed this leaning as a consequence of pre-coordination of the lithiating envoy by the amino side-arm and repulsion effects in the corresponding change-over government. This complexation is also glaring from X-ray construction analyses of the [alpha]-lithiated silanes, which show off intriguing edifice production patterns differing in the species of aggregation and the amount of alkyllithium habituated to. An alternative course to Si-chiral compounds is also presented, which involves desymmetrization of dimethylsilanes mediated by a chiral side-arm. System analyses and computational studies have shown that the diastereoselectivity of this [alpha]-lithiation is influenced by the selectivity of the materialization of the stereogenic nitrogen exploited complexation of the alkyllithium <<>>
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