G-quadruplex DNA-based asymmetric catalysis of michael addition: Effects of sonication, ligands, and co-solvents

Hua Zhao, Kai Shen

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

There is an escalating interest of using double stranded DNA molecules as a chiral scaffold to construct metal-biomacromolecule hybrid catalysts for asymmetric synthesis. Several recent studies also evaluated the use of G-quadruplex DNA-based catalysts for asymmetric Diels-Alder and Friedel-Crafts reactions. However, there is still a lack of understanding of how different oligonucleotides, salts (such as NaCl and KCl), metal ligands and co-solvents affect the catalytic performance of quadruplex DNA-based hybrid catalysts. In this study, we aim to systematically evaluate these key factors in asymmetric Michael addition reactions, and to examine the conformational and molecular changes of DNA by circular dichroism (CD) spectroscopy and gel electrophoresis. We achieved up to 95% yield and 50% enantiomeric excess (ee) when the reaction of 2-acylimidazole 1a and dimethylmalonate was catalyzed by 5'-G3 (TTAG3 )3 -3' (G4DNA1) in 20 mM MOPS (pH 6.5) containing 50 mM KCl and 40 µM [Cu(dmbipy)(NO3 )2 ], and G4DNA1 was pre-sonicated in ice bath for 10 min prior to the reaction. G-quadruplex-based hybrid catalysts provide a new tool for asymmetric catalysis, but future mechanistic studies should be sought to further improve the catalytic efficiency. The current work presents a systematic study of asymmetric Michael addition catalyzed by G-quadruplex catalysts constructed via non-covalent complexing, and an intriguing finding of the effect of pre-sonication on catalytic efficiency.

Original languageEnglish (US)
Pages (from-to)891-898
Number of pages8
JournalBiotechnology Progress
Volume32
Issue number4
DOIs
StatePublished - Jul 8 2016
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2016 American Institute of Chemical Engineers.

Keywords

  • DNA-based hybrid catalyst
  • Michael addition
  • asymmetric catalysis
  • ionic liquid
  • quadruplex DNA

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