Inorganic Chemistry, TU Dortmund University, Otto-Hahn-Straße 6/6a, 44227, Dortmund, Germany.
Center for Mass Spectrometry (CMS), TU Dortmund University, Otto-Hahn-Straße 6/6a, 44227, Dortmund, Germany.
Chemistry. 2023 Jan 2;29(1):e202202935. doi: 10.1002/chem.202202935. Epub 2022 Nov 10.
A silicon-stereogenic aminosilanol was isolated in excellent diastereomeric ratio and the absolute configuration was determined. The silanol is configurative and condensation stable in solution and shows stereoselective transformations with a clean stereospecific pathway in follow-up reactions, which leads to the isolation of a silicon-stereogenic zinc complex and siloxane compounds. Investigations with O-labelled water and mass spectrometry analysis revealed an otherwise hidden exchange of oxygen atoms of silanol and water in solution that proceeds with retention of the configuration at the silicon center. This novel combination of a stereochemical probe and isotopic labeling in a silicon-stereogenic compound opens new analytic possibilities to study stereochemical courses of reactions with the aid of chiral silanols mechanistically.
分离出具有优异非对映选择性的硅手性氨基硅醇，并确定其绝对构型。硅醇在溶液中具有构型和缩合稳定性，并在后续反应中表现出立体选择性转化，具有干净的立体特异性途径，从而分离出硅手性锌配合物和硅氧烷化合物。使用 O 标记水和质谱分析的研究揭示了 otherwise hidden exchange of oxygen atoms of silanol and water in solution that proceeds with retention of the configuration at the silicon center，这在溶液中硅醇和水的氧原子发生 otherwise hidden exchange of oxygen atoms，且保留硅中心的构型。这种在硅手性化合物中结合使用立体化学探针和同位素标记的新方法为借助手性硅醇在机理上研究反应的立体化学过程提供了新的分析可能性。
