通过过渡性西林-西利丁中间体合成静Li(R'3Si) SiC(SiR3) (((1-Ad) 的合成
Lieby Zborovsky1, Roman Dobrovetsky, Mark Botoshansky
1Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.
Journal of the American Chemical Society
|October 24, 2012
概括
研究人员通过THF添加-酸盐合成了新型静化物. 这些由X射线晶体学特征的化合物,揭示了对烯和烯中间体形成和捕获机制的新见解.
科学领域:
- 有机化学 有机化学
- 主群 化学 化学
- 合成无机化学 合成无机化学
背景情况:
- 静化物是含化合物的独特类别,在材料科学和催化中具有潜在的应用.
- 新型低价值物种的合成和表征对于理解的反应性和结合性至关重要.
- 之前的研究已经探讨了silylene和silynes,但它们的受控生成和捕获仍然具有挑战性.
研究的目的:
- 为了合成和描述前两个静化物,Li (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)
- 阐明涉及基酸盐,基试剂和四基 (THF) 的反应机制.
- 为了研究silyne和 silylidene中间体的形成和捕获.
主要方法:
- 通过将THF添加到基酸盐中,合成静化物 (1和2).
- 合成的静化物的结晶.
- 使用X射线晶体学进行结构确定.
- 反应产物分析和密度函数理论 (DFT) 计算,以提出反应机制.
主要成果:
- 成功合成和分离了两种新型静化物,Li (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu) (tBu)) (tBu) (tBu) (tBu) (tBu) (t) (t) (t) (t)
- X射线晶体分析证实了化合物1和2的结构.
- 合成需要协同聚合的酸试剂和THF的存在.
- DFT的计算和产品分析表明,一种机制涉及西拉诺酸的消除,形成一个silyne中间体,重新安排到一个sililidene,随后被silyllithium捕获.
结论:
- 该研究报告了首次合成静化物,扩大了低价值化学的范围.
- 拟议的机制为-酸的反应性和短暂中间体的生成提供了重要的见解.
- 这些发现强调了酸试剂和THF在稳定和捕获反应性物种中的关键作用.
相关概念视频
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Nitriles to Amines: LiAlH4 Reduction
Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
Amides to Amines: LiAlH4 Reduction
Amide reduction with strong reducing agents like lithium aluminum hydride proceeds through a nucleophilic acyl substitution to form amines. Primary, secondary, and tertiary amides yield primary, secondary, and tertiary amines, respectively.
Amide reduction requires two equivalents of the reducing agent, acting as a source of hydride ions. As shown in the figure, the reaction is initiated with a nucleophilic attack by the hydride ion at the carbonyl carbon to form a tetrahedral intermediate.
Amide reduction requires two equivalents of the reducing agent, acting as a source of hydride ions. As shown in the figure, the reaction is initiated with a nucleophilic attack by the hydride ion at the carbonyl carbon to form a tetrahedral intermediate.
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