We report here DNA metalloenzymes that catalyzed the asymmetric Diels–Alder reactions with high conversion, excellent endo/exo selectivities, and enantioselectivities up to −97% ee. Their catalytic-pocket architectures were organized using a rational design strategy based on the Cu(II) ion, the composition of nucleobases, and the incorporation of flexible linkers. Without using the mirror image of B-DNA, DNA metalloenzymes afforded the opposite enantiomer of the Diels–Alder product compared with those obtained using a supramolecular Cu(II)–dmbpy/st–DNA catalyst system. Furthermore, we devised DNA metalloenzymes without the incorporation of an artificial binding ligand and successfully performed Diels–Alder carbon–carbon bond-forming reactions. This study provides a new perspective on the catalytic repertoire of nucleic acids in the realm of protein-dominated metalloenzymes.Keywords: asymmetric catalysis; Cu(II) ion; Diels−Alder reaction; DNA; enantiomeric preference; ligand freedom; metalloenzyme

We have synthesized a fluorescent base analogue, 2-aminothieno[3,4-d]pyrimidine based G-mimic deoxyribonucleoside, 2′-OMe-thG, and investigated its photophysical properties and DNA incorporation. The 2′ methoxy group of 2′-OMe-thG effectively induces the Z-form DNA. Finally we have constructed a visible nanothermometer based on the B–Z transition of DNA using 2′-OMe-thG.

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.Keywords: asymmetric catalysis; direct ligand incorporation; DNA; Friedel−Crafts reaction; hybrid catalyst; intrastrand bipyridine ligand