Supramolecular Modular Approaches to Asymmetric Ca.. (SUPRASYMCAT)
Supramolecular Modular Approaches to Asymmetric Catalysis: Synthesis of Ligands by a Metal-Ligand Mediated Assembly Process
Start date: 09 Jun 2009,
End date: 08 Jun 2011
"Catalysis has been one of the longstanding proposed applications of supramolecular chemistry, which has reached a level of development that allows the practitioner to achieve the design and construction of complex multicomponent assemblies with exquisite detail. Efficient supramolecular systems capable of recognition and catalysis have emerged in recent years, however, the application of supramolecular interactions to generate chiral catalysts is still in its infancy, and reports in the literature are scarce. Our approach focuses on the generation of chiral ligands capable of exploiting supramolecular interactions, and is based on a self-assembly process between the chiral and catalytic components. During the self-assembly process, the chiral information will be transferred from the chiral unit to the catalytic unit and a new supramolecular entity will be formed which will assume the role of the ligand in the asymmetric transformation. The main advantage of this approach rests on the ability to modify the geometry of the catalytic site through non-covalent interactions (hydrogen- and metal-ligand bonding): this geometry will be influenced by the three-dimensional structure of the chiral fragment which is used. Due to the great diversity of possible chiral units, the reactive centre will be able to adopt a range of geometries created by systematic modification of this unit. Our strategy can be easily parallelised to rapidly generate ligand libraries, in which the ligands will preserve most the structural generalities of their predecessors, but it will incorporate “subtle” changes in their three-dimensional structure that will improve the catalytic properties of the assemblies."
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