1,1‘-Binaphthyl based catenanes for asymmetric organocatalysis

Application of mechanically interlocked molecules in asymmetric catalysis is dominated by chiral rotaxanes while chiral catenanes are still underexplored. This is rather surprising as they have several interesting properties that could be exploited in this field as well. Therefore, application of catenanes as chiral catalysts will be investigated in this work. The first part of this thesis deals with the application of catenated and non-catenated chiral phosphoric acids in asymmetric organocatalysis. In more detail, an acyclic and macrocyclic phosphoric acid as well as a bisphosphoric acid catenane are applied as catalysts for the transfer hydrogenation of 2-phenylquinoline. DFT calculations suggested that this catalytic reaction can proceed via two different pathways, a monomeric phosphoric acid pathway and a dimeric phosphoric acid pathway. This hypothesis is tested within this work experimentally by analysing and interpreting kinetic and stereoselectivity data. Special focus lies on the concentration dependent behaviour of the acyclic phosphoric acid (S)-3. In the second part a hetero[2]catenane and a hetero[3]catenane are synthesized using an active metal template method. After further functionalisation, the catenanes are applied in different asymmetric catalytic reactions. Here, two modes of action which exploit the mechanical bond of the catenanes are investigated.


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