Hetero-Sequenced Cage Compounds as Bio-Inspired Molecular Flasks

化学反应的有效催化对现代社会具有重要意义。对于新型催化剂的开发，化学反应的高效催化对现代社会具有十分重要的意义。为了开发新的催化剂，化学家们常常受到自然的启发。天然的催化剂是酶。它们能以极高的精度和效率催化化学反应。反应发生在活性部位，这些活性部位位于受保护的不对称口袋中。虽然大多数活性中心的确切结构是已知的，但它们如何运作的确切方式往往还不够了解。在这个项目中，酶的不对称口袋和活性中心将通过使用模拟的合成化合物来实现。这些模拟物将通过合成新的笼状化合物而获得。这里合成的笼状化合物将提供不对称的空腔，类似于不对称的酶口袋。能够催化化学反应的反应部位将位于那些合成的空腔中。这些空洞将通过应用新的合成概念而获得。通过使用这些新的合成和不对称笼状化合物，它的目标是以前所未有的精度模仿酶。为了模拟酶，这里有两个目标。第一个目标是开发新的催化剂，它应该能够根据它们的大小选择反应伙伴。这种选择是通过笼状化合物进行的。这提供了定义大小的气孔，防止不需要的反应伙伴到达活性中心所在的笼子内部。这种尺寸选择性催化的概念应该应用于有机化合物的氧化。以铁、锰和铜为基础的催化剂将用于氧化反应。大小选择性催化在药物或精细化学品的合成中具有潜在的应用价值。此外，它对原油或生物物质的转化也很重要。第二个目标是更好地了解重要酶的活性部位是如何运作的。为了实现这一点，这些地点的模型将在笼子化合物中重新组装。笼子将保护这些地点，并允许更容易地调查这些地点。我们将特别研究两个非常重要的主题。第一种是铁络合物，它存在于酶中，可以催化许多重要的氧化反应(其中包括青霉素的合成)。第二种是所谓的铁钼辅因子，它可以将氮转化为氨。氨对于生产非常重要的食物是很重要的。在这个项目中获得的知识可能会导致开发更有效的氨合成催化剂。

The efficient catalysis of chemical reactions is of substantial importance to modern society. For the development of new catalysts, The efficient catalysis of chemical reactions is of substantial importance to modern society. For the development of new catalysts, chemists are often inspired by nature.Natures catalysts are enzymes. Those can catalyze chemical reactions with great precision and efficiency. The reactions take at active sites place, which are in protected unsymmetrical pockets located. While the precise structure of most reactive sites is known, their exact way of how they operate is often not sufficiently understood.In this project the unsymmetrical pockets and active sites of enzymes will be through the use of synthetic compounds mimicked. Those mimics will be through the synthesis of new cage compounds obtained. The here synthesized cage compounds will offer unsymmetrical cavities that are similar to the unsymmetrical pockets of enzymes. Reactive sites that can catalyze chemical reactions will be in those synthetic cavities located. The cavities will be through the application of new synthetic concepts obtained. Through the use of these new synthetic and unsymmetrical cage compounds, it is aimed to mimic enzymes with an unprecedented precision. To mimic enzymes follows here two objectives.The first is the development of new catalysts, which should be able to choose their reaction partner based on their size. The selection occurs through the cage compound. This offers pores of a defined size, preventing undesired reaction partner to reach the cage interior where the active center is located. This concept of size-selective catalysis should be applied to the oxidation of organic compounds. Catalysts that are based on iron, manganese and copper will be used for the oxidation reactions. Size-selective catalysis can be of potential interest for the synthesis of pharmaceuticals or fine chemicals. In addition, it is important for the conversion of crude oil or biomass.The second goal is to obtain a better understanding on how active sites of important enzymes operate. To achieve this, models of these sites will be in the cage compounds reassembled. The cages will protect the sites and allow an easier investigation of those. Two very important motifs will be in particular studied. The first is an iron-complex, which is in enzymes that can catalyze many important oxidation reactions (among others the synthesis of penicillin). The second is the so-called iron-molybdenum-cofactor, which can transform nitrogen into ammonia. Ammonia is for the production of food of very high importance. Knowledge gained during this project may lead to the development of more efficient catalysts for ammonia synthesis.