87625-35-2Relevant articles and documents
Selective Si?C(sp3) Bond Cleavage in (Aminomethyl)silanes by Carbanionic Nucleophiles and Its Stereochemical Course
Koller, Stephan G.,Bauer, Jonathan O.,Strohmann, Carsten
supporting information, p. 7991 - 7994 (2017/06/27)
Selective cleavage of a silicon–carbon bond in tetraorganosilanes is still a great challenge. A new type of Si?C(sp3) bond cleavage in bench-stable (aminomethyl)silanes with common organolithium reagents as nucleophiles has now been identified. Suitable leaving groups are benzyl, allyl, and phenylthiomethyl groups. A β-donor function and polar solvents are essential for the reaction. Simple switching between α-deprotonation and substitution is possible through slight modifications of the reaction conditions. The stereochemical course of the reaction was elucidated by using a silicon-chiral benzylsilane. The new transformation proceeds stereospecifically with inversion of configuration and can be used for the targeted synthesis of enantiomerically pure tetraorganosilanes, which are otherwise difficult to access. Quantum chemical calculations provided insight into the mechanism of the new substitution.
NITROGEN-CONTAINING ORGANOSILICON COMPOUNDS. 150. SYNTHESIS AND CHROMATOGRAPHIC AND 1H, 13C, 15N, AND 29Si NMR SPECTROSCOPIC INVESTIGATION OF SUBSTITUTED (PIPERIDINOALKYL)SILANES
Lukevits, E.,Sleiksha, I.,Liepin'sh, E.,Shats-ts, V. D.,Zitsmane, I.,Purvinya, A.
, p. 1319 - 1327 (2007/10/02)
Substituted (piperidinoalkyl)silanes were synthesized and investigated by means of multinuclear NMR spectroscopy and GLC.The data obtained indicate an additional N-Si interaction in α-aminomethylsilanes that depends substantially on the properties of the substituents attached to the silicon atom.The effect of the R1R2R3Si substituent on the capacity of the nitrogen atom for intermolecular interactions is not restricted to steric effects but also has electronic character.
