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

doi:10.1002/chem.201503097

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

Pure And Applied Chemistry

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36 Citations (Scopus)

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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 language	English
Pages (from-to)	1125-1132
Number of pages	8
Journal	Chemistry - A European Journal
Volume	22
Issue number	3
Early online date	11 Dec 2015
DOIs	https://doi.org/10.1002/chem.201503097
Publication status	Published - 18 Jan 2016

Keywords

gold catalysis
hydrophenoxylation of alkynes
alkynes
nucleophiles

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Gomez-Suarez-etal-CEJ-2015-On-the-mechanism-of-the-digold-I-hydroxide-catalyzedAccepted author manuscript, 2.22 MB

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title = "On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes",

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 {\textquoteleft}off-cycle{\textquoteright} rather than an {\textquoteleft}in-cycle{\textquoteright} intermediate.",

keywords = "gold catalysis, hydrophenoxylation of alkynes, alkynes, nucleophiles",

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

note = "This is the peer reviewed version of the following article:Gomez-Suarez, A., Oonishi, Y., Martin, A. R., Vummaleti, S. V. C., Nelson, D. J., Cordes, D. B., ... Poater, A. (2015). On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes. Chemistry - A European Journal, which has been published in final form at: http://dx.doi.org/10.1002/chem.201503097. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.",

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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 journal › Article › peer-review

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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

N1 - This is the peer reviewed version of the following article:Gomez-Suarez, A., Oonishi, Y., Martin, A. R., Vummaleti, S. V. C., Nelson, D. J., Cordes, D. B., ... Poater, A. (2015). On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes. Chemistry - A European Journal, which has been published in final form at: http://dx.doi.org/10.1002/chem.201503097. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

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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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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 3

ER -

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

Abstract

Keywords

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The preference for dual-gold(I) catalysis in the hydro(alkoxylation vs phenoxylation) of alkynes

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