Supramolecular transition metal catalysis Effector controlled catalysis and supramolecular substrate preorganization

Control over the selectivity and reactivity in transition metal catalysis is a major challenge and important for applications in both fine and bulk chemical industries. Traditionally, variation of ligands that coordinate to the metal center has been widely applied and explored to optimize the properties of transition metal catalysts. Despite many breakthroughs, the selectivity and reactivity that are generally dictated by the intrinsic properties of the substrate cannot always meet the requirements for applications. Nature serves as the master of making superior catalysts for versatile transformations. Inspired by nature, we report in this thesis supramolecular tools, i.e. effector controlled catalysis and supramolecular substrate preorganization, to control the selectivities and reactivities in hydroformylation reactions, asymmetric hydrogenation reactions and C-H activation reactions. The supramolecular ligands are readily accessible using rather straight forward protocols, and some of them are rationally design using computational chemistry. Also, the supramolecular catalyst systems are studied in detail using a combination of spectroscopy and DFT calculations to understand the unusual operation manner. These achievements here demonstrate the power of supramolecular interactions in controlling challenging selectivity and reactivity in transition metal-catalyzed transformations, which is crucial for the development of sustainable and efficient chemical transformations.