Next Article in Journal
7-Acetoxycoumarin Inhibits LPS-Induced Inflammatory Cytokine Synthesis by IκBα Degradation and MAPK Activation in Macrophage Cells
Next Article in Special Issue
New Deoxyribozymes for the Native Ligation of RNA
Previous Article in Journal
Sustainable Carbon as Efficient Support for Metal-Based Nanocatalyst: Applications in Energy Harvesting and Storage
Previous Article in Special Issue
Molecular Features and Metal Ions That Influence 10-23 DNAzyme Activity
Open AccessFeature PaperArticle

Covalently Functionalized DNA Duplexes and Quadruplexes as Hybrid Catalysts in an Enantioselective Friedel–Crafts Reaction

Institute of Pharmacy and Molecular Biotechnology, Heidelberg University, 69120 Heidelberg, Germany
*
Author to whom correspondence should be addressed.
Academic Editors: Michael Smietana, Stellios Arseniyadis and Sabine Müller
Molecules 2020, 25(14), 3121; https://doi.org/10.3390/molecules25143121
Received: 26 May 2020 / Revised: 19 June 2020 / Accepted: 2 July 2020 / Published: 8 July 2020
(This article belongs to the Special Issue Advances in Catalytic DNA)
The precise site-specific positioning of metal–ligand complexes on various DNA structures through covalent linkages has gained importance in the development of hybrid catalysts for aqueous-phase homogeneous catalysis. Covalently modified double-stranded and G-quadruplex DNA-based hybrid catalysts have been investigated separately. To understand the role of different DNA secondary structures in enantioselective Friedel–Crafts alkylation, a well-known G-quadruplex-forming sequence was covalently modified at different positions. The catalytic performance of this modified DNA strand was studied in the presence and absence of a complementary DNA sequence, resulting in the formation of two different secondary structures, namely duplex and G-quadruplex. Indeed, the secondary structures had a tremendous effect on both the yield and stereoselectivity of the catalyzed reaction. In addition, the position of the modification, the topology of the DNA, the nature of the ligand, and the length of the linker between ligand and DNA were found to modulate the catalytic performance of the hybrid catalysts. Using the optimal linker length, the quadruplexes formed the (−)-enantiomer with up to 65% ee, while the duplex yielded the (+)-enantiomer with up to 62% ee. This study unveils a new and simple way to control the stereochemical outcome of a Friedel–Crafts reaction. View Full-Text
Keywords: asymmetric catalysis; Friedel–Crafts reaction; hybrid catalysis; covalent modification; DNA asymmetric catalysis; Friedel–Crafts reaction; hybrid catalysis; covalent modification; DNA
Show Figures

Graphical abstract

MDPI and ACS Style

Dey, S.; Jäschke, A. Covalently Functionalized DNA Duplexes and Quadruplexes as Hybrid Catalysts in an Enantioselective Friedel–Crafts Reaction. Molecules 2020, 25, 3121.

Show more citation formats Show less citations formats
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

1
Search more from Scilit
 
Search
Back to TopTop