FWF - CAT - Asymmetric Diels-Alder Reaction: Toward an Ideal Catalyst

Enantioselective homogeneous catalysis represents a broad interdisciplinary research field spanning from biomolecular, organic, inorganic, physical to computational chemistry. The area of transition metal catalysis constitutes an especially appealing way of producing enantiomerically pure compounds, which are very often bioactive and of pharmacological relevance. Despite considerable progress in this field in recent years, there remains much to be achieved and further development and optimization is therefore imperative. In our research proposal, we introduce, based on experimental observations and data (EPR spectroscopy), modern, advanced state of the art theoretical methodology to provide detailed and systematic insight into the intrinsic characteristics of transition metal catalysts. We propose a computational project, which will be focused on the investigations of specific alterations of the ligand sphere around Cu(II) centers in the course of enantioselective Diels-Alder reactions. The goal is to obtain a substantially enhanced knowledge about fundamental aspects of Diels-Alder reactions catalyzed by C2-symmetric Cu(II) complexes and constructing theoretical procedures used for evaluating and designing catalysts of high selectivity, activity and efficiency. Based on recently obtained spectroscopic data and by systematic analysis of the influence of metal centers, ligands, solvent molecules and counterions within the course of catalytic reactions, we want to contribute to the development of optimally performing catalysts by becoming able to predict efficient systems. Main tasks to be addressed in the project: Influence of the counterions on the structure and reactivity of various bis(oxazoline) and bis(sulfoximine) systems. Influence of the solvent on various bis(oxazoline) and related complexes and its impact on the acidity at the Cu(II) center. Influence of various substituents of bis(oxazoline) ring on the activity of the Cu(II) center The computations will be performed in cooperation with the groups of Prof. Martin Kaupp (Technische Universität, Berlin), Prof. Frank Neese (University of Bonn), and Prof. Sason Shaik (Hebrew University of Jerusalem, Israel).