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

Abstract

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.

Metal Ion‐Terpyridine‐Functionalized L‐Tyrosinamide Aptamers: Nucleoapzymes for Oxygen Insertion into CH Bonds and the Transformation of L‐Tyrosinamide into Amidodopachrome

“…A second approach to develop catalytic nucleic acids has involved the functionalization of nucleic acid scaffolds with metal ions or metal ion/ligand complexes as supramolecular homogeneous catalyst assemblies, particularly for chiral synthesis . Different catalytic transformations, such as Michael addition, Friedel–Crafts, and Diels–Alder reactions, were stimulated by these systems. Although chiroselective synthesis by the chiral supramolecular structures was demonstrated, the catalytic turnovers of the systems were low, mainly due to the inefficient binding of substrates to the supramolecular catalyst.…”

Coordination complexes and biomolecules: A wise wedding for catalysis upgrade

“…Finally, Sugiyama and colleagues proposed to graft DNA strands on two points of a bipyridine (Table 1, entry 7 and Scheme 3, middle). Upon metallation and hybridization, the resulting catalyst showed 86% ee for Friedel-Crafts alkylation [60]. The high reaction-specific nature of this strategy is clearly highlighted by the significant differences of enantioselectivities.…”

α,β‐Unsaturated 2‐Acyl‐Imidazoles in Asymmetric Biohybrid Catalysis

“…Park and Sugiyama later developed various synthetic DNA‐based hybrid catalysts containing an intrastrand bipyridine ligand. The latter were prepared by incorporating a 2,2′‐bipyridine‐5,5′‐dicarboxylic acid moiety within a specific 13‐mer ( ODN11 ) or an auto‐complementary single‐strand 29‐mer ( ODN14 ) sequence (Figure ) . The modified 13‐mer oligonucleotide was then associated with a complementary strand containing either a G or a C nucleobase against the ligand and the resulting biohybrid catalysts were evaluated in the intramolecular Friedel‐Crafts alkylation of acyl imidazole 36 .…”

“…The latter were prepared by incorporating a 2,2'bipyridine-5,5'-dicarboxylic acid moiety within a specific 13-mer (ODN11) or an auto-complementary single-strand 29-mer (ODN14) sequence (Figure 17). [59] The modified 13-mer oligonucleotide was then associated with a complementary strand containing either a G or a C nucleobase against the ligand and the resulting biohybrid catalysts were evaluated in the intramolecular Friedel-Crafts alkylation of acyl imidazole 36. As a general trend, the catalysts containing a cytosine facing the bipyridine led to higher selectivities (84 % ee with ODN11/ ODN13 and 86 % ee with the hairpin ODN16 vs 17 % ee with ODN11/ODN12).…”