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

Santeri Aikonen, Mikko Muuronen, Tom Wirtanen, Sami Heikkinen, Joshua Musgreave, Jordi Burés, Juho Helaja

Research output: Contribution to journalArticleScientificpeer-review

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 H-1 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 O-18 labeling experiments. A model for predicting the reactivity from aldehyde frontier molecular orbital energies is also presented.
Original languageEnglish
JournalACS catalysis
Volume8
Issue number2
Pages (from-to)960–967
Number of pages8
ISSN2155-5435
DOIs
Publication statusPublished - 20 Dec 2017
MoE publication typeA1 Journal article-refereed

Fields of Science

  • 116 Chemical sciences

Cite this

Aikonen, Santeri ; Muuronen, Mikko ; Wirtanen, Tom ; Heikkinen, Sami ; Musgreave, Joshua ; Burés, Jordi ; Helaja, Juho. / Gold(I)-Catalyzed 1,3-O-Transposition of Ynones : Mechanism and Catalytic Acceleration with Electron-Rich Aldehydes. In: ACS catalysis. 2017 ; Vol. 8, No. 2. pp. 960–967.
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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 H-1 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 O-18 labeling experiments. A model for predicting the reactivity from aldehyde frontier molecular orbital energies is also presented.",
keywords = "116 Chemical sciences",
author = "Santeri Aikonen and Mikko Muuronen and Tom Wirtanen and Sami Heikkinen and Joshua Musgreave and Jordi Bur{\'e}s and Juho Helaja",
year = "2017",
month = "12",
day = "20",
doi = "10.1021/acscatal.7b04262",
language = "English",
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pages = "960–967",
journal = "ACS catalysis",
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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; Burés, Jordi; Helaja, Juho.

In: ACS catalysis, Vol. 8, No. 2, 20.12.2017, p. 960–967.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Gold(I)-Catalyzed 1,3-O-Transposition of Ynones

T2 - Mechanism and Catalytic Acceleration with Electron-Rich Aldehydes

AU - Aikonen, Santeri

AU - Muuronen, Mikko

AU - Wirtanen, Tom

AU - Heikkinen, Sami

AU - Musgreave, Joshua

AU - Burés, Jordi

AU - Helaja, Juho

PY - 2017/12/20

Y1 - 2017/12/20

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 H-1 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 O-18 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 H-1 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 O-18 labeling experiments. A model for predicting the reactivity from aldehyde frontier molecular orbital energies is also presented.

KW - 116 Chemical sciences

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