Polydentate Lewis acids with oriented acceptor functions

具有定向受体功能的多齿路易斯酸

• 批准号: 248859450
• 负责人: Professor Dr. Norbert W. Mitzel
• 金额: --
• 依托单位: Arbeitsgruppe Anorganische Chemie und Strukturchemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/248859450?language=en
• 关键词: Polydentate; Lewis; acids; oriented; acceptor

Tailor-made structuring of molecular matter allows realizing specific chemical reactivity. Nature demonstrates in manifold ways how concerted spatial placement of reactive functions leads to specific reactivity (usually donor functions or hydrogen bridges). This is also frequently used in synthesis and in the construction of catalysts and receptors. In contrast to the donor functions used in this context (ligand design) examples with defined placement and orientation of acceptor functions (Lewis acids) are still scarce. However, such a concept would enable us to recognize anions and Lewis bases and consequently allow modifying their properties and reactivities. The aim of this project is therefore to place multiple Lewis-acid functions at suitable molecular scaffolds in a defined and oriented way for an optimized binding of Lewis basic substrates. The challenges were so far the very limited accessibility of suitable molecular scaffolds for attaching such functions. They have to be free of Lewis basic units; otherwise they would compete with the substrates for the acidic functions. In the first project period we have developed efficient access to rigid backbone molecules on the basis of hydrocarbons or organosilane scaffold molecules. These include 1,8-functionalized anthracenes, photochemically accessible anthracene dimers with four concordantly oriented functions, photochemically ‘dimerizable’ bridged bis(anthracenes) with switchable selectivities as well as triptycene with three concordantly oriented functions. In addition we found a very elegant synthesis of a syn-anthracen dimer with four alkyne functions pointing into one direction, whose high selectivity is the result of a hydrogen-bridged pre-complex during dimerization. Consequently, it is now clear which of the numerous tested systems provide practicable pathways for the multi-step syntheses to multidentate Lewis-acids, in order to give access to substantial amounts for further experiments aiming at their applications. We have demonstrated for several examples how to attach acceptor functions to these scaffolds. These functions are organometallic units of the elements Al, Ga and In (also Zn and Hg) and electronegatively substituted non-metallic functions of boron and silicon as well as gold functions binding via d10-d10 interactions. In the second project period we intend to bring in the harvest of the work and investment of the first period. We will prepare a variety of new multidentate Lewis-acids and study their chemical properties. These include possibilities of molecular recognition and complexing properties, the ability to enhance the acidity of Lewis acids by complexation with multidentate acceptors (aim ‘super Lewis-acids’), the generation of unusual complexes by chelating dispersive-type interactions, and the use of multidentate Lewis-acids in frustrated Lewis-pair chemistry.

分子物质的定制结构可以实现特定的化学反应性。大自然以多种方式展示了反应功能的协调空间布局如何导致特定的反应性（通常是供体功能或氢桥）。这也经常用于合成以及催化剂和受体的构建。与本文中使用的供体功能（配体设计）相比，具有明确的受体功能（路易斯酸）放置和方向的例子仍然很少。然而，这样的概念将使我们能够识别阴离子和路易斯碱，从而允许改变它们的性质和反应性。因此，该项目的目的是以定义和定向的方式将多个路易斯酸官能团放置在合适的分子支架上，以优化路易斯碱性底物的结合。迄今为止，面临的挑战是用于附加此类功能的合适分子支架的可及性非常有限。它们必须不含路易斯基本单位；否则它们会与底物竞争酸性功能。在第一个项目期间，我们开发了基于碳氢化合物或有机硅烷支架分子的有效获取刚性主链分子的方法。其中包括1,8-官能化蒽、具有四个一致取向功能的光化学可接近的蒽二聚体、具有可切换选择性的光化学“可二聚化”桥联双(蒽)以及具有三个一致取向功能的三蝶烯。此外，我们发现了一种非常优雅的合成方式，具有四个指向一个方向的炔官能团的顺蒽二聚体，其高选择性是二聚过程中氢桥预配合物的结果。因此，现在很清楚，众多测试系统中的哪一个为多齿路易斯酸的多步合成提供了可行的途径，以便为针对其应用的进一步实验提供大量数据。我们已经通过几个例子演示了如何将受体功能附加到这些支架上。这些功能是元素 Al、Ga 和 In（还有 Zn 和 Hg）的有机金属单元以及硼和硅的电负性取代的非金属功能以及通过 d10-d10 相互作用结合的金功能。第二个项目期我们打算把第一期的工作和投资的收获带回来。我们将制备多种新型多齿路易斯酸并研究它们的化学性质。这些包括分子识别和络合特性的可能性，通过与多齿受体络合增强路易斯酸酸性的能力（目标是“超级路易斯酸”），通过螯合分散型相互作用生成不寻常的络合物，以及在受挫路易斯对化学中使用多齿路易斯酸。

项目成果

Syntheses and Structures of 1,8,13,16-Substituted Triptycenes

1,8,13,16-取代三蝶烯的合成和结构

• DOI: 10.1002/ejoc.201800770
• 发表时间: 2018
• 期刊: European Journal of Organic Chemistry
• 影响因子: 2.8
• 作者: A. Schwartzen;M. Rovers;B. Neumann;H.-G. Stammler;N. W. Mitzel
• 通讯作者: N. W. Mitzel

A Rational Approach to Tetra‐Functional Photo‐Switches

• DOI: 10.1002/open.201900029
• 发表时间: 2019-03
• 期刊: ChemistryOpen
• 影响因子: 2.3
• 作者: Philipp Niermeier;Jan-Hendrik Lamm;A. Mix;B. Neumann;H. Stammler;N. Mitzel

Syntheses, Solid State Structures and Photochemistry of α,ω-Bis-[(1,8-dichloroanthracen-10-yl)dimethylsilyl]alkanes

α,β-双-[(1,8-二氯蒽-10-基)二甲基甲硅烷基]烷烃的合成、固态结构和光化学

• DOI: 10.1055/s-0037-1610128
• 发表时间: 2018
• 期刊: Synthesis
• 作者: P. Niermeier;J.-H. Lamm;M. Linnemannstöns;B. Neumann;H.-G. Stammler;N. W. Mitzel
• 通讯作者: N. W. Mitzel

Zweizähnige Bor-Lewis-Säuren und ihre Selektivität in der Wirt-Gast-Komplexbildung

双齿硼路易斯酸及其在主客体络合物形成中的选择性

• DOI: 10.1002/anie.201812696
• 发表时间: 1969
• 期刊: Angewandte Chemie
• 作者: P. Niermeier;S. Blomeyer;Y. K. J. Bejaoui;J. L. Beckmann;B. Neumann;H.-G. Stammler;N. W. Mitzel
• 通讯作者: N. W. Mitzel