[2012年08月16日]

 

Enantioselective Diels–Alder Reactions with G-Quadruplex DNA-Based Catalysts 

 

 

    We found that human telomeric G-quadruplex DNA (ht-G4DNA) shows enantioselective catalytic performance in the Diels-Alder reaction and Friedel-Crafts reaction, and the research results were recently published in the journals Angew. Chem. Int. Ed. (DOI: 10.1002/anie.201204850) and Chem. Commun. (DOI: 10.1039/C2CC31320K).

    DNA is known as the genetic material of the living organisms, which generally exists in duplex structure in nature. Normally, DNA has not been regarded as a catalytic species owing to its stable double-stranded scaffold. Once the single-stranded DNA is dissociated from its complementary partner strand, it could form a catalytically competent tertiary structure, such as G4DNA. We observed that ht-G4DNA alone can catalyze the enantioselective Diels-Alder reaction and Friedel-Crafts reaction. When an artificial G4DNA metalloenzyme is assembled between G4DNA and Cu2+ ions, reactivity and enantioselectivity of the reactions can be significantly enhanced. In addition, we found that the configuration of the enantiomer is sensitive to the conformation of G4DNA. Taking Diels-Alder reaction as an example, the absolute configuration of the Diels-Alder product can be reversed when the conformation of G4DNA is switched from antiparallel to parallel. Both the reaction rate and the enantioselectivity of the Diels-Alder reaction were found to be dependent on the DNA sequence.

    Natural biological catalysts usually include protein enzymes and RNA enzymes, whereas DNA is solely as a genetic material. Nevertheless, the chemical similarity between RNA and DNA inspired the exploration on DNA as a catalyst. In 1994, Breaker and Joyce reported that an artificial DNAzyme can catalyze the cleavage of a single ribonucleotide. Recently, a DNA-based catalyst composed of double-stranded DNA and metal complex has been reported by Roelfes and Feringa to be active for asymmetric reactions. However, whether DNA itself exerts enantioselective catalytic function is still an open question. In our research, we observed that ht-G4DNA shows enantioselective catalytic performance, which might provide an inspiration in exploring the catalytic function of DNA.

    This work was financially supported by the National Natural Science Foundation of China.

  

Article
Enantioselective Diels–Alder Reactions with G-Quadruplex DNA-Based Catalysts
Changhao Wang, Guoqing Jia, Jun Zhou, Yinghao Li, Yan Liu, Shengmei Lu and Can Li*
Angew. Chem. Int. Ed., 2012, DOI: 10.1002/anie.201204850.
http://onlinelibrary.wiley.com/doi/10.1002/anie.201204850/pdf

Enantioselective Friedel–Crafts reactions in water catalyzed by a human telomeric G-quadruplex DNA metalloenzyme
Changhao Wang, Yinghao Li, Guoqing Jia, Yan Liu, Shengmei Lu and Can Li*
Chem. Commun., 2012, 48, 6232-6234.
http://pubs.rsc.org/en/content/articlelanding/2012/CC/c2cc31320k

 

 

 

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