On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes

Adrián Gómez-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 Gómez-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

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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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Original language	English (US)
Pages (from-to)	1125-1132
Number of pages	8
Journal	Chemistry - A European Journal
Volume	22
Issue number	3
DOIs	https://doi.org/10.1002/chem.201503097
State	Published - Dec 13 2015

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@article{9411477a6236420ba0b1015dbf713c64,

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. {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

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 = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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 = "2015",

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doi = "10.1002/chem.201503097",

language = "English (US)",

volume = "22",

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journal = "Chemistry - A European Journal",

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T1 - On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes

AU - Gómez-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 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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 - 2015/12/13

Y1 - 2015/12/13

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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DO - 10.1002/chem.201503097

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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

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CCDC 1030163: Experimental Crystal Structure Determination : (mu-phenolato)-bis(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)-di-gold tetrafluoroborate dichloromethane solvate

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On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes

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CCDC 1030163: Experimental Crystal Structure Determination : (mu-phenolato)-bis(1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)-di-gold tetrafluoroborate dichloromethane solvate

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