Hybrid catalysts
The range of reactions which RNA can catalyze is limited because of the paucity of functional groups carried by nucleotides compared to amino acids in proteins. In order to expand the scope of RNA-based catalysis, we are currently investigating ways to complement the catalytic properties of RNA with the rich reactivity of transition metal complexes. Our goal is to generate what we call hybrid catalysts, i. e. conjugates of nucleic acids and transition metals that can perform asym-metric catalysis in aqueous medium. Our strategy relies on in vitro selection of active sequences from random pools of nucleic acids. This requires the development of new synthetic methods for the functionalisation of oligonucleotides with metal-binding moieties. We are currently developing hybrid catalysts for important organometallic transformations (like allylic substitution and conjugate addition to enones) catalysed by rhodium, iridium or palladium. We expect to establish a completely novel approach to asymmetric catalysis in water where the stereocontrol of the reaction is determined by a folded nucleic acid.
This project encompasses many different fields from organometallic catalysis and organic synthesis to molecular biology.
References:
- Fiammengo et al. J. Am. Chem. Soc. 2005 (127) 9271.
- Caprioara et al. Chem. Eur. J. 2007 (13) 2089.
- Fournier et al., Angew. Chem. Int. Ed. 2009 (48) 4426; Angew. Chem. 2009 (121) 4490.
