Weak Interaction in Stabilized Silylcations

在催化过程中小分子和低活性化合物的活化是现代合成化学的中心任务之一。这项任务具有根本意义和实际意义，特别是考虑到社会未来的主要挑战，例如组织即将到来的氢经济或将二氧化碳转化为有机材料。建议的研究提案的目的是合成定制的硅烷基阳离子化合物具有特殊的，但控制的反应性。提出了一种分子测试系统，以确定、建立和测试允许有效控制甲硅烷基阳离子化合物反应性的参数。这些模型体系将作为催化剂应用于几种有机模型反应和小分子活化化学，如二氢裂解，二氧化碳转化或C-F键活化。作为一个特别有趣的功能，建议的甲硅烷基阳离子系统具有潜在的手性。因此，本提案的一个主要目标是手性甲硅烷基阳离子的产生和研究，以努力将其固有的高反应性与对映选择性过程联合收割机结合起来。手性硅基阳离子作为高效的刘易斯酸催化剂在有机合成中的应用对不对称选择性有机合成具有重要影响。因此，温和的反应条件将是有利的，并且反应性较低的化合物的反应将变得可行。

The activation of small molecules and less-reactive compounds in catalytic processes is one of the central tasks of modern synthetic chemistry. This task is of fundamental interest as well as of practical significance, in particular in view of central future challenges for society such as the organization of a forthcoming hydrogen economy or carbon dioxide conversion into organic materials. Purpose of the suggested research proposal is the synthesis of tailor-made silyl cationic compounds with exceptional but controlled reactivity. A molecular test system is suggested to identify, to establish and to test the parameters that allow efficient control over the reactivity of the silyl cationic compounds. These model systems will be applied as catalysts in several organic model reactions and in small molecule activation chemistry such as dihydrogen cleavage, carbon dioxide conversion or C-F bond activation. As a particular interesting feature, the suggested silyl cationic systems have the potential for chirality. Therefore, a major objective of this proposal is the generation and investigation of chiral silyl cations in an effort to combine their inherent high reactivity with enantioselective processes. The use of chiral silyl cations as efficient Lewis acid catalysts in organic transformations could have significant impact on enantioselective organic synthesis. Hereby milder reaction conditions would be favored and reactions of less reactive compounds would become feasible.