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

Adrián Gõmez-Suárez; 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-catalysed hydrophenoxylation of alkynes

Adrián Gõmez-Suárez, 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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}₂(μ-OH)][BF₄] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of 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

Alkynes
Density functional calculations
Gold
Homogeneous catalysis
Hydrophenoxylation
Reaction mechanisms

Access to Document

10.1002/chem.201503097

Upgrade Small Equipment Base: Small items of research equipment at the University of St Andrews. Supporting a new generation of physical sciences research
Woollins, J. D. (PI)
EPSRC
1/11/12 → 31/03/13
Project: Standard
FUNCAT: EU FP7 ERC Advanced Grant - FUNCAT - Fundamental Studies in Organometallic Chemistry and Homogeneous Catalysis
Nolan, S. P. (PI)
European Research Council
1/01/09 → 31/12/14
Project: Standard

On the mechanism of the digold(I)-hydroxide-catalysed hydrophenoxylation of alkynes (dataset)
Cordes, D. B. (Creator) & Slawin, A. M. Z. (Creator), Cambridge Crystallographic Data Centre, 2020
https://dx.doi.org/10.5517/ccdc.csd.cc13kz2q and 16 more links, https://dx.doi.org/10.5517/cc10pbxy, https://dx.doi.org/10.5517/cc10pbyz, https://dx.doi.org/10.5517/cc10pbz0, https://dx.doi.org/10.5517/cc10pc02, https://dx.doi.org/10.5517/cc10p887, https://dx.doi.org/10.5517/cc10p898, https://dx.doi.org/10.5517/cc10p8b9, https://dx.doi.org/10.5517/cc10p8cb, https://dx.doi.org/10.5517/cc10p8dc, https://dx.doi.org/10.5517/cc10p8fd, https://dx.doi.org/10.5517/cc10pbtv, https://dx.doi.org/10.5517/cc10pbwx, https://dx.doi.org/10.5517/cc10pc13, https://dx.doi.org/10.5517/cc10pc24, https://dx.doi.org/10.5517/cc10pc35, https://dx.doi.org/10.5517/cc10pc46 (show fewer)
Dataset

Cite this

@article{e4e0d7a4adbe4e628e1ed9cac7d5d6a7,

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

abstract = "Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of 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.",

keywords = "Alkynes, Density functional calculations, Gold, Homogeneous catalysis, Hydrophenoxylation, Reaction mechanisms",

author = "Adri{\'a}n G{\~o}mez-Su{\'a}rez 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 = "The ERC (Advanced Investigator Award-FUNCAT), EPSRC, and Syngenta are gratefully acknowledged for support. Umicore AG is acknowledged for their generous gift of materials. S.P.N. and L.C. thank the King Abdullah University of Science and Technology (CCF project) for support. Y.O. thanks the Uehara Memorial Foundation for a Research Fellowship. A.P. thanks the Spanish MINECO (project CTQ2014-59832-JIN and FEDER grant UNGI10-4E-801 and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900).",

year = "2016",

month = jan,

day = "18",

doi = "10.1002/chem.201503097",

language = "English",

volume = "22",

pages = "1125--1132",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley & Sons, Ltd",

number = "3",

}

TY - JOUR

T1 - On the mechanism of the digold(I)-hydroxide-catalysed hydrophenoxylation of alkynes

AU - Gõmez-Suárez, Adrián

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 - The ERC (Advanced Investigator Award-FUNCAT), EPSRC, and Syngenta are gratefully acknowledged for support. Umicore AG is acknowledged for their generous gift of materials. S.P.N. and L.C. thank the King Abdullah University of Science and Technology (CCF project) for support. Y.O. thanks the Uehara Memorial Foundation for a Research Fellowship. A.P. thanks the Spanish MINECO (project CTQ2014-59832-JIN and FEDER grant UNGI10-4E-801 and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900).

PY - 2016/1/18

Y1 - 2016/1/18

N2 - Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of 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 by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of 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 - Alkynes

KW - Density functional calculations

KW - Gold

KW - Homogeneous catalysis

KW - Hydrophenoxylation

KW - Reaction mechanisms

U2 - 10.1002/chem.201503097

DO - 10.1002/chem.201503097

M3 - Article

AN - SCOPUS:84954026529

SN - 0947-6539

VL - 22

SP - 1125

EP - 1132

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 3

ER -

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

Abstract

Keywords

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Projects

Upgrade Small Equipment Base: Small items of research equipment at the University of St Andrews. Supporting a new generation of physical sciences research

FUNCAT: EU FP7 ERC Advanced Grant - FUNCAT - Fundamental Studies in Organometallic Chemistry and Homogeneous Catalysis

Datasets

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

Cite this