Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center

Matthew J. Harper; Christopher J. Arthur; John Crosby; Edward J. Emmett; Rosalyn L. Falconer; Andrew J. Fensham-Smith; Paul J. Gates; Thomas Leman; John E. McGrady; John F. Bower; Christopher A. Russell

doi:10.1021/jacs.8b01411

Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center

Matthew J. Harper, Christopher J. Arthur, John Crosby, Edward J. Emmett, Rosalyn L. Falconer, Andrew J. Fensham-Smith, Paul J. Gates, Thomas Leman, John E. McGrady^*, John F. Bower, Christopher A. Russell

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal)

37 Citations (Scopus)

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Abstract

Three-coordinate bipyridyl complexes of gold, [(κ²-bipy)Au(η²-C₂H₄)][NTf₂], are readily accessed by direct reaction of 2,2′-bipyridine (bipy), or its derivatives, with the homoleptic gold ethylene complex [Au(C₂H₄)₃][NTf₂]. The cheap and readily available bipyridyl ligands facilitate oxidative addition of aryl iodides to the Au(I) center to give [(κ²-bipy)Au(Ar)I][NTf₂], which undergo first aryl-zinc transmetalation and second C-C reductive elimination to produce biaryl products. The products of each distinct step have been characterized. Computational techniques are used to probe the mechanism of the oxidative addition step, offering insight into both the origin of the reversibility of this process and the observation that electron-rich aryl iodides add faster than electron-poor substrates. Thus, for the first time, all steps that are characteristic of a conventional intermolecular Pd(0)-catalyzed biaryl synthesis are demonstrated from a common monometallic Au complex and in the absence of directing groups.

Original language	English
Pages (from-to)	4440-4445
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	140
Issue number	12
Early online date	19 Mar 2018
DOIs	https://doi.org/10.1021/jacs.8b01411
Publication status	Published - 28 Mar 2018

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10.1021/jacs.8b01411

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Harper, M. J., Arthur, C. J., Crosby, J., Emmett, E. J., Falconer, R. L., Fensham-Smith, A. J., Gates, P. J., Leman, T., McGrady, J. E., Bower, J. F., & Russell, C. A. (2018). Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center. Journal of the American Chemical Society, 140(12), 4440-4445. https://doi.org/10.1021/jacs.8b01411

Harper, Matthew J. ; Arthur, Christopher J. ; Crosby, John ; Emmett, Edward J. ; Falconer, Rosalyn L. ; Fensham-Smith, Andrew J. ; Gates, Paul J. ; Leman, Thomas ; McGrady, John E. ; Bower, John F. ; Russell, Christopher A. / Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 12. pp. 4440-4445.

@article{b657197cb9444249bc058b4fdfa71373,

title = "Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center",

abstract = "Three-coordinate bipyridyl complexes of gold, [(κ2-bipy)Au(η2-C2H4)][NTf2], are readily accessed by direct reaction of 2,2′-bipyridine (bipy), or its derivatives, with the homoleptic gold ethylene complex [Au(C2H4)3][NTf2]. The cheap and readily available bipyridyl ligands facilitate oxidative addition of aryl iodides to the Au(I) center to give [(κ2-bipy)Au(Ar)I][NTf2], which undergo first aryl-zinc transmetalation and second C-C reductive elimination to produce biaryl products. The products of each distinct step have been characterized. Computational techniques are used to probe the mechanism of the oxidative addition step, offering insight into both the origin of the reversibility of this process and the observation that electron-rich aryl iodides add faster than electron-poor substrates. Thus, for the first time, all steps that are characteristic of a conventional intermolecular Pd(0)-catalyzed biaryl synthesis are demonstrated from a common monometallic Au complex and in the absence of directing groups.",

author = "Harper, {Matthew J.} and Arthur, {Christopher J.} and John Crosby and Emmett, {Edward J.} and Falconer, {Rosalyn L.} and Fensham-Smith, {Andrew J.} and Gates, {Paul J.} and Thomas Leman and McGrady, {John E.} and Bower, {John F.} and Russell, {Christopher A.}",

year = "2018",

month = mar,

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doi = "10.1021/jacs.8b01411",

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Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center. / Harper, Matthew J.; Arthur, Christopher J.; Crosby, John; Emmett, Edward J.; Falconer, Rosalyn L.; Fensham-Smith, Andrew J.; Gates, Paul J.; Leman, Thomas; McGrady, John E.; Bower, John F.; Russell, Christopher A.

In: Journal of the American Chemical Society, Vol. 140, No. 12, 28.03.2018, p. 4440-4445.

Research output: Contribution to journal › Article (Academic Journal)

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T1 - Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2′-Bipyridyl-Ligated Gold Center

AU - Harper, Matthew J.

AU - Arthur, Christopher J.

AU - Crosby, John

AU - Emmett, Edward J.

AU - Falconer, Rosalyn L.

AU - Fensham-Smith, Andrew J.

AU - Gates, Paul J.

AU - Leman, Thomas

AU - McGrady, John E.

AU - Bower, John F.

AU - Russell, Christopher A.

PY - 2018/3/28

Y1 - 2018/3/28

N2 - Three-coordinate bipyridyl complexes of gold, [(κ2-bipy)Au(η2-C2H4)][NTf2], are readily accessed by direct reaction of 2,2′-bipyridine (bipy), or its derivatives, with the homoleptic gold ethylene complex [Au(C2H4)3][NTf2]. The cheap and readily available bipyridyl ligands facilitate oxidative addition of aryl iodides to the Au(I) center to give [(κ2-bipy)Au(Ar)I][NTf2], which undergo first aryl-zinc transmetalation and second C-C reductive elimination to produce biaryl products. The products of each distinct step have been characterized. Computational techniques are used to probe the mechanism of the oxidative addition step, offering insight into both the origin of the reversibility of this process and the observation that electron-rich aryl iodides add faster than electron-poor substrates. Thus, for the first time, all steps that are characteristic of a conventional intermolecular Pd(0)-catalyzed biaryl synthesis are demonstrated from a common monometallic Au complex and in the absence of directing groups.

AB - Three-coordinate bipyridyl complexes of gold, [(κ2-bipy)Au(η2-C2H4)][NTf2], are readily accessed by direct reaction of 2,2′-bipyridine (bipy), or its derivatives, with the homoleptic gold ethylene complex [Au(C2H4)3][NTf2]. The cheap and readily available bipyridyl ligands facilitate oxidative addition of aryl iodides to the Au(I) center to give [(κ2-bipy)Au(Ar)I][NTf2], which undergo first aryl-zinc transmetalation and second C-C reductive elimination to produce biaryl products. The products of each distinct step have been characterized. Computational techniques are used to probe the mechanism of the oxidative addition step, offering insight into both the origin of the reversibility of this process and the observation that electron-rich aryl iodides add faster than electron-poor substrates. Thus, for the first time, all steps that are characteristic of a conventional intermolecular Pd(0)-catalyzed biaryl synthesis are demonstrated from a common monometallic Au complex and in the absence of directing groups.

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