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Catalysis with Chalcogen Bonds.

Sebastian BenzJavier López-AndariasJiri MaredaNaomi SakaiStefan Matile
Published in: Angewandte Chemie (International ed. in English) (2016)
Herein, we introduce catalysts that operate with chalcogen bonds. Compared to conventional hydrogen bonds, chalcogen bonds are similar in strength but more directional and hydrophobic, thus ideal for precision catalysis in apolar solvents. For the transfer hydrogenation of quinolines and imines, rate enhancements well beyond a factor of 1000 are obtained with chalcogen bonds. Better activities with deeper σ holes and wider bite angles, chloride inhibition and correlation with computed anion binding energies are consistent with operational chalcogen bonds. Comparable to classics, such as 2,2'-bipyrroles or 2,2'-bipyridines, dithieno[3,2-b;2',3'-d]thiophenes (DTTs), particularly their diimides, but also wide-angle cyclopentadithiazole-4-ones are identified as privileged motifs to stabilize transition states in the focal point of the σ holes on their two co-facial endocyclic sulfur atoms.
Keyphrases
  • ionic liquid
  • transition metal
  • high resolution
  • magnetic resonance imaging
  • density functional theory
  • transcription factor
  • molecular dynamics
  • binding protein
  • metal organic framework
  • aqueous solution