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Desymmetrization and Parallel Kinetic Resolution of 1-Ethynylcyclobutanols via Asymmetric Cooperative Gold Catalysis.

Ke ZhaoZiguang YangJielin YangXinyi LiCarlos D QuintanillaLiming Zhang
Published in: Journal of the American Chemical Society (2023)
Enantioselective gold catalysis remains a challenging area of research. By harnessing gold-ligand cooperation in the presence of a chiral bifunctional phosphine ligand featuring a novel 3'-phosphine oxide moiety, highly enantioselective desymmetrization of 1-ethynylcyclobutanols is achieved, permitting access to chiral α-methylenecyclopentanones featuring a diverse array of chiral quaternary and tertiary centers. This cooperative gold catalysis also enables parallel kinetic resolution in gold catalysis, delivering cyclopentanone regioisomers with excellent enantiomeric excesses. DFT calculations of the transition states support the distinct mechanism of asymmetric induction via controlling the conformation of the bound substrate and hence dictating the ring bond undergoing migration.
Keyphrases
  • capillary electrophoresis
  • silver nanoparticles
  • ionic liquid
  • molecular dynamics simulations
  • single molecule
  • visible light
  • high resolution
  • high throughput
  • big data
  • transition metal