Rational perturbation of the fluorescence quantum yield in emission-tunable and predictable fluorophores (Seoul-Fluors) by a facile synthetic method involving C-H activation

Angew Chem Int Ed Engl. 2014 Jan 27;53(5):1346-50. doi: 10.1002/anie.201308826. Epub 2014 Jan 20.

Abstract

Fluorescence imaging enables the uniquely sensitive observation of functional- and molecular-recognition events in living cells. However, only a limited range of biological processes have been subjected to imaging because of the lack of a design strategy and difficulties in the synthesis of biosensors. Herein, we report a facile synthesis of emission-tunable and predictable Seoul-Fluors, 9-aryl-1,2-dihydrolopyrrolo[3,4-b]indolizin-3-ones, with various R(1) and R(2) substituents by coinage-metal-catalyzed intramolecular 1,3-dipolar cycloaddition and subsequent palladium-mediated CH activation. We also showed that the quantum yields of Seoul-Fluors are controlled by the electronic nature of the substituents, which influences the extent of photoinduced electron transfer. On the basis of this understanding, we demonstrated our design strategy by the development of a Seoul-Fluor-based chemosensor 20 for reactive oxygen species that was not accessible by a previous synthetic route.

Keywords: CH activation; fluorescence; fluorophore design; quantum yield; switchable sensors.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbon / chemistry
  • Catalysis
  • Cycloaddition Reaction
  • Electron Transport
  • Fluorescent Dyes / chemical synthesis*
  • Fluorescent Dyes / chemistry
  • Heterocyclic Compounds, 4 or More Rings / chemical synthesis*
  • Heterocyclic Compounds, 4 or More Rings / chemistry
  • Hydrogen / chemistry
  • Palladium / chemistry
  • Pyrroles / chemical synthesis*
  • Pyrroles / chemistry
  • Quantum Theory
  • Reactive Oxygen Species / chemistry

Substances

  • Fluorescent Dyes
  • Heterocyclic Compounds, 4 or More Rings
  • Pyrroles
  • Reactive Oxygen Species
  • Palladium
  • Carbon
  • Hydrogen
  • pyrroloindolizine