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

  • External authors:
  • Santeri Aikonen
  • Mikko Muuronen
  • Tom Wirtanen
  • Sami Heikkinen
  • Joshua Musgreave
  • Juho Helaja

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Gold(I)-catalyzed 1,3-O-transposition of ynones: Mechanism and catalytic acceleration with electron rich aldehydes. / Aikonen, Santeri; Muuronen, Mikko; Wirtanen, Tom; Heikkinen, Sami; Musgreave, Joshua; Bures Amat, Jorge; Helaja, Juho.

In: ACS Catalysis, Vol. 8, 2018, p. 960-967.

Research output: Contribution to journalArticle

Harvard

Aikonen, S, Muuronen, M, Wirtanen, T, Heikkinen, S, Musgreave, J, Bures Amat, J & Helaja, J 2018, 'Gold(I)-catalyzed 1,3-O-transposition of ynones: Mechanism and catalytic acceleration with electron rich aldehydes', ACS Catalysis, vol. 8, pp. 960-967. https://doi.org/10.1021/acscatal.7b04262

APA

Aikonen, S., Muuronen, M., Wirtanen, T., Heikkinen, S., Musgreave, J., Bures Amat, J., & Helaja, J. (2018). Gold(I)-catalyzed 1,3-O-transposition of ynones: Mechanism and catalytic acceleration with electron rich aldehydes. ACS Catalysis, 8, 960-967. https://doi.org/10.1021/acscatal.7b04262

Vancouver

Author

Aikonen, Santeri ; Muuronen, Mikko ; Wirtanen, Tom ; Heikkinen, Sami ; Musgreave, Joshua ; Bures Amat, Jorge ; Helaja, Juho. / Gold(I)-catalyzed 1,3-O-transposition of ynones: Mechanism and catalytic acceleration with electron rich aldehydes. In: ACS Catalysis. 2018 ; Vol. 8. pp. 960-967.

Bibtex

@article{aac048219a5346599a73f99de99ba400,
title = "Gold(I)-catalyzed 1,3-O-transposition of ynones: Mechanism and catalytic acceleration with electron rich aldehydes",
abstract = "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.",
author = "Santeri Aikonen and Mikko Muuronen and Tom Wirtanen and Sami Heikkinen and Joshua Musgreave and {Bures Amat}, Jorge and Juho Helaja",
year = "2018",
doi = "10.1021/acscatal.7b04262",
language = "English",
volume = "8",
pages = "960--967",
journal = "A C S Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",

}

RIS

TY - JOUR

T1 - Gold(I)-catalyzed 1,3-O-transposition of ynones: Mechanism and catalytic acceleration with electron rich aldehydes

AU - Aikonen, Santeri

AU - Muuronen, Mikko

AU - Wirtanen, Tom

AU - Heikkinen, Sami

AU - Musgreave, Joshua

AU - Bures Amat, Jorge

AU - Helaja, Juho

PY - 2018

Y1 - 2018

N2 - 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.

AB - 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.

U2 - 10.1021/acscatal.7b04262

DO - 10.1021/acscatal.7b04262

M3 - Article

VL - 8

SP - 960

EP - 967

JO - A C S Catalysis

JF - A C S Catalysis

SN - 2155-5435

ER -