Weak Interaction in Stabilized Silylcations

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，特别是考虑到社会今后面临的主要挑战，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。建议的研究方案的目的是合成具有特殊但可控反应活性的定制硅基阳离子化合物。建议建立一个分子测试系统来识别、建立和测试允许有效控制硅基阳离子化合物的反应性的参数。这些模型体系将作为催化剂应用于多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特征，所建议的硅基阳离子体系具有手性的潜力。因此，这一建议的一个主要目标是生成和研究手性硅基阳离子，以努力将其固有的高反应性与对映选择性过程相结合。手性硅基阳离子作为高效的Lewis酸催化剂在有机转化中的应用将对不对称有机合成产生重大影响。因此，较温和的反应条件将是有利的，活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.