Dispersion Interaction in Metal- and Organocatalysis - Assessment and Implementation in Salalen Ligands and N-Heterocyclic Carbenes

了解-量化-使用：我们的研究旨在评估和实施两个小分子均相催化领域的分散控制：(I)钛-Salalen络合物用于非官能化特别是末端烯烃与过氧化氢的不对称环氧化；(Ii)N-杂环卡宾用于有机催化中的Umpolung反应和作为金属催化的C-H活化中的配体。通过在两个催化剂系统中引入分散能量供体(DEDS)，在第一个资助期期间，这两个领域都取得了重大的实验进展和机理洞察。对于第二个资助期，我们打算在这些信息的基础上，通过合理的方法，提供新的、容易获得和广泛适用的催化剂。机械论研究的目的将是彻底了解它们的行动模式，特别是分散的作用。这种多层次的方法一方面有助于我们理解分子催化转化的分散控制。另一方面，通过合理地加入分散元素，我们的目标是开发出具有前所未有的活性和选择性的新型催化剂。该项目将以协同的方式结合合成、光谱学、机械分析和量子化学计算。与其他研究小组的几项合作是这一努力不可或缺的一部分。

Understand - quantify - use: Our studies aim at the assessment and implementation of dispersion control in two areas of small-molecule homogeneous catalysis: (i) titanium-salalen complexes for the asymmetric epoxidation of non-functionalized and in particular terminal olefins with hydrogen peroxide, and (ii) N-heterocyclic carbenes for Umpolung reactions in organocatalysis and as ligands in metal-catalyzed C-H activation. By the introduction of dispersion energy donors (DEDs) into the two catalyst systems, significant experimental progress and mechanistic insight was achieved in both areas in the course of the first funding period. For the second funding period, we are intending to build on this body of information, and to provide, by rational approach, novel, readily available and broadly applicable catalyst generations. Mechanistic studies will aim at a thorough understanding of their modes of action, and in particular of the role of dispersion. This multi-level approach is intended to contribute, on one hand, to our understanding of dispersion control of molecular catalytic transformations. On the other hand, by rational incorporation of dispersion elements, we are aiming at novel catalyst generations of unprecedented activity and selectivity. The project will combine, in a synergistic manner, synthesis, spectroscopy, mechanistic analyses, and quantum-chemical computation. Several cooperations with other research groups are integral part of this endeavor.