Anorganische Chemie, Technische Universität Dortmund, Otto-Hahn-Straße 6, 44227 Dortmund, Germany.
J Am Chem Soc. 2015 Apr 8;137(13):4304-7. doi: 10.1021/jacs.5b00861. Epub 2015 Mar 30.
Intramolecular isomerization in pentacoordinate compounds can play an essential role for the adjustment of defined stereochemical information. Here, we present a conclusive mechanism of a stereocontrolled reaction on chiral dimethoxysilanes that opens new aspects in understanding the origin of creating silicon-centered chirality during a nucleophilic substitution process. By combining experimental, structural, and quantum chemical methods, we were able to disclose an interconversion process, based on consecutive Berry-type motions, as the most plausible mechanism for describing the stereochemical outcome in suchlike substitution reactions.
分子内异构化在五配位化合物中可以起到调整特定立体化学信息的重要作用。在这里，我们提出了手性二甲氧基硅烷的立体控制反应的明确机制，这为理解亲核取代过程中产生硅中心手性的起源提供了新的方面。通过结合实验、结构和量子化学方法，我们能够揭示出一种基于连续 Berry 型运动的互变过程，作为描述此类取代反应立体化学结果的最合理机制。
