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Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones.

Lin ZhangKen YamazakiJamie A LeitchRubén ManzanoVictoria A M AtkinsonTrevor A HamlinDarren J Dixon
Published in: Chemical science (2020)
The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles via an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a copper(i) co-catalyst to deliver the stereodefined bicyclic core, is described. Successful application to oxygen analogues was also achieved, thereby providing a new enantioselective synthetic entry to architecturally complex bicyclic ethereal frameworks. The mechanistic pathway and the origin of enantio- and diastereoselectivities has been uncovered using density functional theory (DFT) calculations.
Keyphrases
  • density functional theory
  • molecular dynamics
  • ionic liquid
  • molecular docking
  • room temperature
  • gold nanoparticles
  • metal organic framework
  • capillary electrophoresis