DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

Almudena García-Fernández, Rik P. Megens, Lara Villarino , Gerard Roelfes*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

40 Citations (Scopus)
22 Downloads (Pure)

Abstract

DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a reaction that critically depends on the >700- to 990-fold rate acceleration caused by the presence of a DNA scaffold. The DNA-induced rate acceleration observed is the highest reported due to the environment presented by a biomolecular scaffold for any hybrid catalyst, to date. Based on a combination of kinetics and binding studies, it is proposed that the rate acceleration is in part due to the DNA acting as a pseudophase, analogous to micelles, in which all reaction components are concentrated, resulting in a high effective molarity. The involvement of additional second coordination sphere interactions is suggested by the enantioselectivity of the product. The results presented here show convincingly that the DNA-based catalysis concept, thanks to the DNA-accelerating effect, can be an effective approach to achieving a chemically challenging reaction in water.

Original languageEnglish
Pages (from-to)16308-16314
Number of pages7
JournalJournal of the American Chemical Society
Volume138
Issue number50
DOIs
Publication statusPublished - 21-Dec-2016

Keywords

  • DIELS-ALDER REACTION
  • ASYMMETRIC CATALYSIS
  • ENANTIOSELECTIVE PROTONATION
  • ARTIFICIAL METALLOENZYMES
  • 1,4-ADDITION/ENANTIOSELECTIVE PROTONATION
  • ENOLATE PROTONATIONS
  • MICHAEL ADDITION
  • LEWIS-ACID
  • COMPLEXES
  • ESTERS

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