由LiClCl介导的二化物转化为化
Debabrata Mukherjee1, Arkady Ellern, Aaron D Sadow
1Department of Chemistry and U.S. Department of Energy Ames Laboratory, Iowa State University, Ames, Iowa 50011, USA.
Journal of the American Chemical Society
|May 18, 2010
概括
使用 (II) 和化 (LiCl) 的新型β消除反应产生了活性-键. 这种反应在协同作用下使用Li(+) 和Cl(-) 离子形成化和环.
科学领域:
- 有机金属化学 有机金属化学
- 化学 化学 化学
- 协调化学 协调化学
背景情况:
- Disilazido化合物是无机合成中已知的前体.
- 金属化物在有机金属化合物中介反应中的作用尚未完全理解.
- 激活Si-H键对于开发新的合成方法至关重要.
研究的目的:
- 为了研究一种不寻常的β-消除反应,涉及 (II) 和LiCl.
- 阐明Li(+) 和Cl(-) 离子在反应机制中的协同作用.
- 为了描述由disilazido化合物与LiCl.Cl反应而形成的产品.
主要方法:
- 协调和的disilazido化合物与THF/toluene混合物中的LiCl的反应.
- 形成含有活性SiH分子的添加物.
- 由此产生的化和环化产品的表征.
主要成果:
- 在LiCl和disilazido化合物之间形成的添加物激活SiH部分.
- 在THF/toluene中,添加物转化为化和环化.
- ((+) 和Cl ((-) 离子协同作用,因为没有一个离子单独促进β-消除.
- 这种反应代表了正式的β消除途径.
结论:
- ((+) 和Cl ((-) 的协同作用对于观察到的β-消除反应至关重要.
- 这项研究揭示了通过LiCl调解的disilazido化合物的新反应途径.
- 这些发现有助于理解性金属化物对有机金属反应机制的影响.
相关概念视频
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The mechanism proceeds in three steps. First, the nucleophilic hydride ion attacks the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs as a leaving group, generating an aldehyde. A second nucleophilic attack by the hydride yields an alkoxide ion, which, upon protonation, gives a primary alcohol as...
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Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
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As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic acid...
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