On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes

Adrian Gomez-Suarez, Yoshihiro Oonishi, Anthony R. Martin, Sai V. C. Vummaleti, David J. Nelson, David B. Cordes, Alexandra M. Z. Slawin, Luigi Cavallo, Steven P. Nolan, Albert Poater

Research output: Contribution to journalArticle

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Abstract

Herein we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes, using both experimental and computational methods. The dissociation of [{Au(NHC)}2(µ-OH)][BF4] is essential to enter the catalytic cycle; this step is favored in the presence of bulky, non-coordinating counterions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but as a co-catalyst, lowering the energy barriers for several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an ‘off-cycle’ rather than an ‘in-cycle’ intermediate.
Original languageEnglish
Pages (from-to)1125-1132
Number of pages8
JournalChemistry - A European Journal
Volume22
Issue number3
Early online date11 Dec 2015
DOIs
Publication statusPublished - 18 Jan 2016

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Gems
Alkynes
Energy barriers
Computational methods
Phenol
Potential energy
Gold
Phenols
Catalysts
hydroxide ion

Keywords

  • gold catalysis
  • hydrophenoxylation of alkynes
  • alkynes
  • nucleophiles

Cite this

Gomez-Suarez, A., Oonishi, Y., Martin, A. R., Vummaleti, S. V. C., Nelson, D. J., Cordes, D. B., ... Poater, A. (2016). On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes. Chemistry - A European Journal, 22(3), 1125-1132. https://doi.org/10.1002/chem.201503097
Gomez-Suarez, Adrian ; Oonishi, Yoshihiro ; Martin, Anthony R. ; Vummaleti, Sai V. C. ; Nelson, David J. ; Cordes, David B. ; Slawin, Alexandra M. Z. ; Cavallo, Luigi ; Nolan, Steven P. ; Poater, Albert. / On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes. In: Chemistry - A European Journal. 2016 ; Vol. 22, No. 3. pp. 1125-1132.
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Gomez-Suarez, A, Oonishi, Y, Martin, AR, Vummaleti, SVC, Nelson, DJ, Cordes, DB, Slawin, AMZ, Cavallo, L, Nolan, SP & Poater, A 2016, 'On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes', Chemistry - A European Journal, vol. 22, no. 3, pp. 1125-1132. https://doi.org/10.1002/chem.201503097

On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes. / Gomez-Suarez, Adrian; Oonishi, Yoshihiro; Martin, Anthony R.; Vummaleti, Sai V. C.; Nelson, David J.; Cordes, David B.; Slawin, Alexandra M. Z.; Cavallo, Luigi; Nolan, Steven P.; Poater, Albert.

In: Chemistry - A European Journal, Vol. 22, No. 3, 18.01.2016, p. 1125-1132.

Research output: Contribution to journalArticle

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AU - Gomez-Suarez, Adrian

AU - Oonishi, Yoshihiro

AU - Martin, Anthony R.

AU - Vummaleti, Sai V. C.

AU - Nelson, David J.

AU - Cordes, David B.

AU - Slawin, Alexandra M. Z.

AU - Cavallo, Luigi

AU - Nolan, Steven P.

AU - Poater, Albert

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PY - 2016/1/18

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N2 - Herein we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes, using both experimental and computational methods. The dissociation of [{Au(NHC)}2(µ-OH)][BF4] is essential to enter the catalytic cycle; this step is favored in the presence of bulky, non-coordinating counterions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but as a co-catalyst, lowering the energy barriers for several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an ‘off-cycle’ rather than an ‘in-cycle’ intermediate.

AB - Herein we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes, using both experimental and computational methods. The dissociation of [{Au(NHC)}2(µ-OH)][BF4] is essential to enter the catalytic cycle; this step is favored in the presence of bulky, non-coordinating counterions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but as a co-catalyst, lowering the energy barriers for several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an ‘off-cycle’ rather than an ‘in-cycle’ intermediate.

KW - gold catalysis

KW - hydrophenoxylation of alkynes

KW - alkynes

KW - nucleophiles

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DO - 10.1002/chem.201503097

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SP - 1125

EP - 1132

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 3

ER -