36147-17-8Relevant academic research and scientific papers
Stereoselective synthesis of silicon-stereogenic aminomethoxysilanes: Easy access to highly enantiomerically enriched siloxanes
Bauer, Jonathan O.,Strohmann, Carsten
, p. 720 - 724 (2014)
A route towards the synthesis of N,O-functionalized silicon-stereogenic organosilanes with excellent optical purities has been developed. Investigations into the stereoconvergence and configurational stability of an aminomethoxysilane suggest a kinetically controlled multistep substitution mechanism. Selective exchange of the Si-N bond by a second Si-O bond builds the basis for the controlled formation of chiral siloxane units with different oxygen-containing functional groups. Subsequent reactions of the chiral aminomethoxysilanes with hydroxy groups support a general inversion mechanism at the asymmetrically substituted silicon atom of N,O-functionalized organosilanes. Broad access to silicon-stereogenic N,O-functionalized organosilanes in optically pure form is provided by a highly chemo- and diastereoselective substitution on aminodimethoxysilanes. The novel compounds could be further transformed stereoselectively with alcohols and a silanol and are predestined as building blocks for a controlled development of chiral siloxane units. Copyright
Synthesis and Hydrogen-Bond Patterns of Aryl-Group Substituted Silanediols and -triols from Alkoxy- and Chlorosilanes
Kannengie?er, Jan-Falk,Briesenick, Max,Meier, Dennis,Huch, Volker,Morgenstern, Bernd,Kickelbick, Guido
, p. 16461 - 16476 (2021/10/25)
Organosilanols typically show a high condensation tendency and only exist as stable isolable molecules under very specific steric and electronic conditions at the silicon atom. In the present work, various novel representatives of this class of compounds were synthesized by hydrolysis of alkoxy- or chlorosilanes. Phenyl, 1-naphthyl, and 9-phenanthrenyl substituents at the silicon atom were applied to systematically study the influence of the aromatic substituents on the structure and reactivity of the compounds. Chemical shifts in 29Si NMR spectroscopy in solution, correlated well with the expected electronic situation induced by the substitution pattern on the Si atom. 1H NMR studies allowed the detection of strong intermolecular hydrogen bonds. Single-crystal X-ray structures of the alkoxides and the chlorosilanes are dominated by π-π interactions of the aromatic systems, which are substituted by strong hydrogen bonding interactions representing various structural motifs in the respective silanol structures.
