Gold(I)-Catalyzed 1,3-O-Transposition of Ynones: Mechanism and Catalytic Acceleration with Electron-Rich Aldehydes

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, anal...

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Published inACS catalysis Vol. 8; no. 2; pp. 960 - 967
Main Authors Aikonen, Santeri, Muuronen, Mikko, Wirtanen, Tom, Heikkinen, Sami, Musgreave, Joshua, Burés, Jordi, Helaja, Juho
Format Journal Article
LanguageEnglish
Published American Chemical Society 02.02.2018
Subjects
variable time normalization analysis (VTNA)
reaction kinetics
DFT
gold catalysis
mechanism
ynone
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Summary: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 could be achieved by the addition of a substoichiometric amount of electron-rich aldehyde as a mediator, allowing the gold-catalyzed 1,3-O-transposition of terminal ynones to ynaldehydes. The mechanism is further supported by NMR characterization of the acetal intermediate and 18O labeling experiments. A model for predicting the reactivity from aldehyde frontier molecular orbital energies is also presented.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.7b04262