Elias Selmi Higashi
Project title: Innovative DNA-based asymmetric photocatalysis
Summary: While initially based on peptides and protein scaffolds, the construction of artificial metalloenzymes has recently been extended to nucleic acids, which have the advantage of being able to adopt a plethora of secondary or even more complex tertiary structures and exhibit high chemical stability. Most importantly, the recent developments made in the field of oligonucleotide synthesis allow a rapid and inexpensive access to custom-made oligonucleotides of specific sequences, while the predictable nature of nucleic acid hybridization offers a simple and cutting edge platform to program assemblies with emerging functions. Since the pioneering work of Roelfes and Feringa a little bit over a decade ago, a few groups around the world including ours have exploited the power of DNA in asymmetric catalysis, allowing for the development of a handful of highly selective processes. This project aims at extending the concept of DNA based asymmetric catalysis (DAC) to new synthetic transformations with a special emphasis given to the challenging field of asymmetric photocatalysis. Ultimately, we wish to develop a platform of new artificial DNA-based hybrid catalysts with specific reactivities capable of selectively converting small organic molecules into more complex chiral structures upon photo-irradiation. In this context, the project aims at moving beyond the expertise we’ve established in the field by 1) developing new photocatalyzed reactions through a careful design of DNA/ligand systems, 2) developing sustainable catalysts based on recyclable solid-supported oligonucleotides, which will ultimately be implemented to large scale continuous flow processes, and 3) apply all these tools to the synthesis of biologically active natural products.