DNA-based catalysis and micellar catalysis

PhD ceremony: Ms. F. Rosati, 14.45 uur, Aula Academiegebouw, Broerstraat 5, Groningen

Dissertation: DNA-based catalysis and micellar catalysis

Promotor(s): prof. G. Roelfes and prof. B.L. Feringa

Faculty: Mathematics and Natural Sciences

 

In this thesis the use of the DNA molecule as a chiral scaffold for enantioselective catalysis was discussed. The intrinsic chirality of the DNA is transferred within a metal catalyzed reaction resulting in an excess of one of the enantiomers of the product. It has been shown that the assembly of DNA-based catalysts allows for excellent selectivity and enantioselectivity in several metal catalyzed reactions in water. Initially, the focus was on DNA-based catalysts from ligands of the first generation (which involve a metal binding domain, a spacer and a DNA-interacting moiety) in two reactions: the enantioselective CuII-catalyzed Diels-Alder reaction and the asymmetric CuII-catalyzed syn-hydration of enones in water, a reaction for which no equivalent in conventional catalysis exists. The role of DNA in the observed catalysis and enantioselectivity was defined for both reactions and the attempts to improve the design and the performance of the catalysts were reported.

In the second part of the thesis the concept of micellar catalysis was introduced. A recent application which involved the use of an anionic surfactant in combination with a copper salt in order to achieve a dramatic acceleration of the Friedel-Craft reaction in water was presented.

Lastly, the use of DNA as a promising tool to achieve control over the geometry and the location of the catalyst in space in the presence of a micellar aggregate, and to tune its activity, was described.

All together, the results demonstrate the great potential of DNA in catalysis and supramolecular chemistry.