Development of DNA-Based Hybrid Catalysts through Direct Ligand Incorporation: Toward Understanding of DNA-Based Asymmetric Catalysis

We have developed a DNA-based hybrid catalyst containing an intrastrand bipyridine ligand through direct ligand incorporation and successfully performed asymmetric intramolecular Friedel–Crafts alkylations. This is the first report on the DNA hybrid catalyst system where an intrastrand ligand is covalently introduced into the phosphate backbone. We have generated a series of active site to investigate the structural details of DNA hybrid catalysts and demonstrated that catalytic properties of DNA hybrid catalysts are governed by the disposition of the metal-binding site in the DNA duplex, the size of catalytic cavity, and the composition of nucleobases in the catalytic pocket.