(9c) Asymmetric Catalysis with Artificial Metalloenzymes Based on dsDNA-Amphiphiles | AIChE

(9c) Asymmetric Catalysis with Artificial Metalloenzymes Based on dsDNA-Amphiphiles


Wang, D. - Presenter, Johns Hopkins University
Guo, J., Johns Hopkins University
Kuang, H., Johns Hopkins University
Tsapatsis, M., Johns Hopkins University
Kokkoli, E., Johns Hopkins University
DNA-based artificial metalloenzymes (ArMs), with the accommodation of catalytically active transition metals into the unique chiral microenvironment of DNA scaffolds, have been widely investigated in the field of asymmetric catalysis. However, due to the solubility limitation of DNA, most of the reactions catalyzed by DNA-ArMs happen in water, where more hydrophobic reactants have low solubility. By conjugating different hydrophobic tails to DNA sequences, we designed the first example of ArMs based on double-stranded DNA (dsDNA)-amphiphiles that bind to the copper (II) complex of 4,4’-dimethyl-2,2’-bipyridine, and can catalyze highly enantioselective Diels-Alder reactions. The amphiphilic dsDNA-ArMs demonstrated faster kinetics and higher enantioselectivity at smaller concentrations compared to the non-amphiphilic dsDNA-ArM, in both water and water-methanol mixtures. This behavior was attributed to the ability of the dsDNA-amphiphiles to self-assemble in different solvents and create a favorable environment for the synthesis of chiral products.