Development of DNA Metalloenzymes Using a Rational Design Approach and Application in the Asymmetric Diels–Alder Reaction

Park, Soyoung; Okamura, Izumi; Sakashita, Sohei; Yum, Ji Hye; Acharya, Chiranjit; Gao, Li; Sugiyama, Hiroshi

doi:10.1021/acscatal.5b01046

Cited by 48 publications

(27 citation statements)

References 40 publications

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“…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.…”

Section: Introductionmentioning

confidence: 99%

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

Luo

Biniuri

Vázquez‐González

et al. 2019

Adv Funct Materials

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A series of metal ion-terpyridine-modified L-tyrosinamide aptamers (M n+ = Cu 2+ or Fe 3+ ) act as enzyme-mimicking catalysts (nucleoapzymes) for oxygen-insertion into CH bonds and the transformation of L-tyrosinamide into amidodopachrome. The reaction proceeds in the presence of H 2 O 2 and coadded L-ascorbic acid. In one series of experiments, the catalyzed oxidation of L-tyrosinamide to amidodopachrome by a set of nucleoapzymes consisting of Fe 3+ -or Cu 2+ -terpyridine complexes tethered directly or through a 4 × thymidine (4 × T) bridge, to the 5′-or 3′-end of the 49-mer L-tyrosinamide aptamer or to a shorter 23-mer L-tyrosinamide aptamer is examined. All nucleoapzymes reveal catalytic Michaelis-Menten enzyme-like activities and the separated Fe 3+ -or Cu 2+ -terpyridine and L-tyrosinamide aptamer units show only minute catalytic properties. The catalytic activities of the nucleoapzymes are attributed to the concentration of the L-tyrosinamide substrate by the aptamer units in proximity to the catalytic sites (K d = (14 ± 0.1) × 10 −6 m for all 49-mer catalysts and K d = (2.5 ± 0.1) × 10 −6 m and K d = (0.8 ± 0.04) × 10 −6 m for the 23-mer catalysts). Electron spin resonance experiments reveal that •OH radicals and ascorbate radicals participate in the transformation of tyrosine derivatives to catechol products. An autocatalytic feedback mechanism for the amplified generation of the two radicals is suggested.

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Section: Introductionmentioning

confidence: 99%

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

Luo

Biniuri

Vázquez‐González

et al. 2019

Adv Funct Materials

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“…This limitation prevents prediction and detailed understanding of the factors that determine activity and selectivity. To overcome these problems, a specific covalent attachment strategy is an alternative in which the transition‐metal‐ligand complex is covalently attached to DNA, allowing to more precisely localize the metal binding center and to study the structure–function relationship …”

Section: Introductionmentioning

confidence: 99%

Catalysis of Michael Additions by Covalently Modified G‐Quadruplex DNA

Dey

Rühl

Jäschke

2017

Chemistry A European J

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Enantioselective catalysis utilizing G-quadruplex DNA-based artificial metalloenzymes has emerged as a new approach in the field of aqueous-phase homogeneous catalysis. Recently, a catalytic asymmetric Michael addition employing a covalently modified G-quadruplex in combination with Cu ions has been reported. Here we assess, by systematic chemical variation and using various spectrometric techniques, a variety of parameters that govern rate acceleration and stereoselectivity of the reaction, such as the position of modification, the topology of the quadruplex, the nature of the ligand, the length of the linker between ligand and DNA, the chemical identity of monovalent ions and transition metal complexes. The DNA quadruplex modified at position 10 (dU10) with hexynyl-linked bpy ligand showed twice the initial reaction rate as compared with the DNA strand derivatized at position 12 (dU12). The strikingly different dependence of the stereoselectivity on the linker length, and their different spectroscopic properties indicate large differences in the architecture of the catalytic centers between the dU10-derivatized and the dU12-modified quadruplexes. Upon addition of Cu , both types of bpy-derivatized DNA strands form defined 1:1 Cu-DNA complexes stable enough for mass spectrometric analysis, while the underivatized strands exhibit weak and unspecific binding, correlated with much lower catalytic rate acceleration. Both dU10- and dU12-derivatized quadruplexes could be reused ten times without reduction of stereoselectivity.

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“…Hence, various counter‐strands incorporating a triethylene glycol ( ODN15a ) or an alkyl linker ( ODN15b and ODN15c ) opposite to cytosine were prepared and evaluated in the Diels‐Alder reaction between both α,β‐unsaturated 2‐acyl imidazole 8 and α,β‐unsaturated 2‐acyl pyridine 11 and cyclopentadiene ( 23 ). The best results were obtained with the triethylene glycol linker which afforded ee values ranging between 88 and 92 % (Figure ) …”

Section: Dna‐based Asymmetric Catalysismentioning

confidence: 99%

“…The best results were obtained with the triethylene glycol linker which afforded ee values ranging between 88 and 92 % ( Figure 18). [60]…”

Section: Covalent Approachmentioning

confidence: 99%

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

et al. 2019

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α,β-Unsaturated acylimidazoles have been used in a plethora of enantioselective transformations over the years and have unsurprisingly become privileged building blocks for asymmetric catalysis. Interestingly however, their use in asymmetric biohybrid catalysis as bidentate substrates able to interact with artificial metalloenzymes has only recently emerged, expanding considerably in the last few years. Easy to prepare and to posttransform, α,β-unsaturated acylimidazoles appear as leading synthons for the asymmetric construction of CÀ C and CÀ O bonds. This Minireview highlights the current and increasing interest of these key building blocks in the context of asymmetric biohybrid catalysis with the aim to stimulate further research into their still unexploited potential. The use of these α,β-unsaturated acylimidazoles in metal-catalyzed and organocatalyzed transformations will be covered in a back-to-back Minireview

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Development of DNA Metalloenzymes Using a Rational Design Approach and Application in the Asymmetric Diels–Alder Reaction

Cited by 48 publications

References 40 publications

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

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

Catalysis of Michael Additions by Covalently Modified G‐Quadruplex DNA

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

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