Gold(I)-catalyzed 1,3-O-transposition of ynones: Mechanism and catalytic acceleration with electron rich aldehydes

@article{Aikonen2018GoldIcatalyzed1O,
  title={Gold(I)-catalyzed 1,3-O-transposition of ynones: Mechanism and catalytic acceleration with electron rich aldehydes},
  author={Santeri Aikonen and Mikko Muuronen and Tom Wirtanen and S. Heikkinen and Joshua Musgreave and Jordi Bur{\'e}s and Juho Helaja},
  journal={ACS Catalysis},
  year={2018},
  volume={8},
  pages={960-967}
}
The gold-catalyzed 1,3-O-transposition of ynones occurs intermolecularly via a cyclic organo-gold acetal intermediate formed from the nucleophilic oxo attack of a second ynone, i.e. either starting material or product, on a gold-activated ynone. The combination of 1H NMR monitored kinetic data, analyzed using variable time normalization analysis (VTNA) and kinetic modeling, and density functional theory (DFT) was used to elucidate the mechanism. A significant acceleration of the reaction rate… Expand
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