原生锂酰胺选择性烷氧基硅烷取代的机理研究:从单取代到二取代和三取代si - n功能化硅烷

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Jan-Lukas Kirchhoff, Tristan Mairath, Mara Schöler, Robin Risken and Carsten Strohmann*, 
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引用次数: 0

摘要

用锂酰胺选择性取代有机硅烷中的甲氧基为氨基功能化硅烷提供了一条直接途径。虽然氯硅烷通常用于这种转化,但其高反应活性和低选择性限制了合成控制。在这里,我们重点研究了甲氧基硅烷,并评估了它们对伯电锂酰胺的取代行为。采用原位傅里叶变换红外光谱(FTIR)和密度泛函理论(DFT)计算相结合的方法,阐明了单取代的机理,并确定了总反应阶数和活化能等关键动力学参数。基于这些发现,开发了控制二取代和三取代的反应条件。不同的替代结果可以被不同的潜在机制途径合理化。溶剂效应和锂酰胺聚集态在其中起关键作用。这项工作为设计具有合成相关性的选择性Si-O到si - n替代策略提供了一个机制框架。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Mechanistic Investigations of Selective Alkoxysilane Substitutions by Primary Lithium Amides: From Mono- to Di- and Trisubstituted Si–N-Functionalized Silanes

Mechanistic Investigations of Selective Alkoxysilane Substitutions by Primary Lithium Amides: From Mono- to Di- and Trisubstituted Si–N-Functionalized Silanes

Mechanistic Investigations of Selective Alkoxysilane Substitutions by Primary Lithium Amides: From Mono- to Di- and Trisubstituted Si–N-Functionalized Silanes

Selective substitution of methoxy groups in organosilanes by lithium amides provides a direct route to amino-functionalized silanes. While chlorosilanes are commonly used in such transformations, their high reactivity and low selectivity limit synthetic control. Here, we focus on methoxysilanes and evaluate their substitution behavior toward primary lithium amides. Using a combination of in situ Fourier-transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations, we elucidate the mechanism of the monosubstitution and identify key kinetic parameters such as overall reaction order and activation energy. Based on these findings, reaction conditions were developed to achieve controlled di- and trisubstitution. The distinct substitution outcomes could be rationalized by different underlying mechanistic pathways. Solvent effects and lithium amide aggregation states were found to play a critical role. This work provides a mechanistic framework for designing selective Si–O to Si–N-substitution strategies with synthetic relevance.

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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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