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The Rational Development of Organometallic Reagents through Fluorescence Microscopy Experiments

通过荧光显微镜实验合理开发有机金属试剂

基本信息

批准号：
405360690
负责人：
Dr. Kristof Jess
金额：
--
依托单位：
Department of Chemistry
依托单位国家：
德国
项目类别：
Research Fellowships
财政年份：
2018
资助国家：
德国
起止时间：
2017-12-31 至 2018-12-31
项目状态：
已结题

来源：
https://gepris.dfg.de/gepris/projekt/405360690?language=en
关键词：
Rational Development Organometallic Reagents through

项目摘要

The key objective of the project is to answer long-standing questions about how additives facilitate the formation of organometallic reagents. To achieve this objective, fluorescence microscopy approaches with sensitivity for the detection of single molecules of organometallic intermediates will be developed. Organometallic reagents are important for the synthesis of complex organic compounds, e.g., natural products and pharmaceuticals. A simple route to such reagents is the formation of a metal and an organohalide species. However, this simple route is often only possible using certain additives. For example, Blum's research group has recently discovered that lithium chloride helps to dissolve organozinc reagents from the zinc surface, using a highly sensitive microscopy approach. The key experiment is the visualization of small quantities of surface organometallic intermediates by fluorescence microscopy and the determination of the conditions under which these species are observed. The quantity of these intermediates is too low to be detected by traditional analytical instrumentation. Through the development of imaging agents for this approach, I aim to answer four questions: (A) Organometallic reagents of manganese and aluminum require catalytic amounts of metal salts (chlorides of titanium, indium, lead, or bismuth). However, the mechanism of action of these additives is still unclear. Five mechanistic possibilities will be considered and investigated by fluorescence microscopy.(B) An alternative route to organometallic reagents is the synthesis from so-called Rieke metals – finely divided and highly reactive metal powders. It has been shown that the synthetic route towards Rieke metals has an impact on their reactivity; the difference in reactivity is believed to be caused by by-products formed in each synthesis. Here, I want to investigate why Rieke metals from different routes have different reactivities, by determining the role of the by-products directly.(C) The origin of pronounced solvent effects in the formation of organozinc reagents will be determined.(D) Two practical applications are proposed through rational reaction design: 1) enabling the simple and safer synthesis of organotin reagents – important reagents in the Stille coupling and 2) improvement of the synthetically important Ullmann coupling.Conclusion: The intended research will help to understand the mechanistic role of additives in organometallic reagent synthesis for organic and organometallic chemistry. In the future, this understanding may enable the preparation of organometallic reagents from commercial metal powders for a significantly larger range of metals. At the same time, fluorescence microscopy will be developed as a new analytical method in inorganic chemistry.

该项目的主要目标是回答长期存在的关于添加剂如何促进有机金属试剂形成的问题。为了实现这一目标，荧光显微镜的方法与灵敏度检测的有机金属中间体的单分子将被开发。有机试剂对于复杂有机化合物的合成是重要的，例如，天然产品和药物。一个简单的路线，这样的试剂是形成的金属和有机卤化物物种。然而，这种简单的路线通常只能使用某些添加剂。例如，Blum的研究小组最近发现，氯化锂有助于从锌表面溶解有机锌试剂，使用高度灵敏的显微镜方法。关键实验是通过荧光显微镜观察少量表面有机金属中间体，并确定观察这些物质的条件。这些中间体的量太低，无法用传统的分析仪器检测。通过开发这种方法的成像剂，我的目标是回答四个问题：（A）锰和铝的有机试剂需要催化量的金属盐（钛，铟，铅或铋的氯化物）。然而，这些添加剂的作用机制仍不清楚。五个机制的可能性将被考虑和研究荧光显微镜。(B)有机金属试剂的另一种途径是从所谓的Rieke金属-精细分散和高反应性的金属粉末合成。已经表明，Rieke金属的合成路线对其反应性有影响;反应性的差异被认为是由每次合成中形成的副产物引起的。在这里，我想通过直接确定副产物的作用来研究为什么来自不同路线的Rieke金属具有不同的反应性。(C)将确定有机锌试剂形成中明显的溶剂效应的起源。(D)通过合理的反应设计，提出了两个实际应用：1）使简单和安全的合成有机锡试剂-重要的试剂在Stille偶联和2）改进的合成重要Ullmann coupling.Conclusion：预期的研究将有助于理解添加剂在有机和有机金属化学的有机金属试剂合成的机理作用。在未来，这种理解可能使从商业金属粉末制备有机金属试剂的金属范围显着更大。同时，荧光显微镜也将发展成为无机化学中一种新的分析方法。