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

金属和有机催化中的分散相互作用 - Salalen 配体和 N-杂环卡宾的评估和实施

• 批准号: 271340972
• 负责人: Professor Dr. Albrecht Berkessel
• 金额: --
• 依托单位: Institut für Anorganische und Analytische Chemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/271340972?language=en
• 关键词: Dispersion; Interaction; Metal; Organocatalysis; Assessment

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.

理解-量化-用途：我们的研究旨在评估和实施小分子均相催化的两个领域中的分散控制：（i）钛-salalen络合物，用于非官能化的，特别是末端烯烃与过氧化氢的不对称环氧化，和（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。通过在两种催化剂体系中引入分散能供体（DEDs），在第一个资助期内，在这两个领域都取得了显著的实验进展和机理见解。对于第二个供资期，我们打算在这一信息基础上，通过合理的方法提供新颖、现成和广泛适用的催化剂代。机理研究的目的是彻底了解它们的作用方式，特别是分散的作用。这种多层次的方法是为了有助于，一方面，我们的理解分散控制的分子催化转化。另一方面，通过合理引入分散元素，我们的目标是获得具有前所未有的活性和选择性的新型催化剂。该项目将联合收割机，以协同的方式，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奋进的组成部分。