超分子相互作用是外消旋解析的关键:索默(1R,2S,5R)-甲基(1-萘基)-苯基薄荷硅烷的(SSi)-和(RSi)-非对映异构体的新见解

Jan-Lukas Kirchhoff, Carsten Strohmann
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引用次数: 0

摘要

通过使用不同的分析工具对 Sommer 等人提出的两种非对映生硅薄荷硅烷--(RSi)-3 和 (SSi)-3 进行详细研究,建立了一种高产率的高选择性方法。单晶 X 射线衍射分析用于研究不同的结晶速度,而 Hirshfeld 表面分析则用于扩展固态超分子相互作用,结果表明结晶速度更快的非对映异构体 (SSi)-3 具有更强的氢桥。此外,通过 DFT 计算还发现两种非对映异构体的基态能量相似。随后的核磁共振研究显示,Si-构型稳定,在 110 °C 下超过 4 小时后才开始发生外延。只需使用天然存在的 (-)- 薄荷醇作为试剂,就能以高产率和高立体化学纯度获得立体硅中心构型相反的两种非对映异构体。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Supramolecular Interactions as Key in Racemic Resolution: New Insights into the (SSi)‐ and (RSi)‐Diastereomers of (1R,2S,5R)‐Methyl(1‐naphthyl)‐phenylmenthoxy­silane of Sommer
A highly selective approach with high yields of two diastereomeric silicon‐stereogenic menthoxysilanes, (RSi)‐3 and (SSi)‐3, introduced by Sommer et al., could be established as well as investigated in detail using different analytical tools. Single‐crystal X‐ray diffraction analysis was used to examine the different crystallization rates while Hirshfeld surface analysis was applied to extend supramolecular interactions in the solid state which showed stronger hydrogen bridges for the faster crystallizing diastereomer (SSi)‐3. In addition, similar ground‐state energies have been found for both diastereomers by DFT calculations. Subsequent NMR studies showed stable Si‐configurations wherein epimerization only started after more than 4 hours at 110 °C. Access to both diastereomers with opposite configuration at the stereogenic silicon center is achievable in high yields and high stereochemical purity using only naturally occurring (–)‐menthol as a reagent.
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