Stereocontrol in Nucleophilic Substitution Reactions at Silicon: The Role of Permutation in Generating Silicon-Centered Chirality
Stereocontrol in Nucleophilic Substitution Reactions at Silicon: The Role of Permutation in Generating Silicon-Centered Chirality
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DOI：
10.1021/jacs.5b00861
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发表时间：
2015-04-08
影响因子：
15
通讯作者：
Strohmann, Carsten
中科院分区：
文献类型：
--
作者：
Bauer, Jonathan O.;Strohmann, Carsten
五配位化合物的分子内异构化对于确定的立体化学信息的调整起着至关重要的作用。在这里，我们提出了一个决定性的机制，手性二甲氧基硅烷的立体控制反应，打开了新的方面，在理解的起源创造硅为中心的手性在亲核取代过程中。通过结合实验，结构和量子化学方法，我们能够揭示一个相互转换过程，连续的贝里型运动的基础上，作为最合理的机制来描述立体化学的结果在suchlike取代反应。
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.