Gold-Catalyzed Cycloisomerizations of Enynes: A Mechanistic Perspective

Jiménez‐Núñez, Eloísa; Echavarren, Antonio M.

doi:10.1021/cr0684319

Cited by 1,975 publications

(172 citation statements)

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“…Calculations confirmed that this reaction was endothermic and had a high activation energy. In contrast, products resulting from oxidative addition were observed both with a mono-ligated Au I complex 10 (2) and a trinuclear Au cluster 12 (3). Calculations showed that both reactions were now exothermic and the activation barrier was lower, but much strongly so in the case of the cluster.…”

Section: Methodsmentioning

confidence: 96%

“…[2] Nowadays, cyclizations and cycloisomerizations based on gold catalysis constitute some of the best methods for a rapid access to molecules with complex carbon skeleton. [3] Recently, the versatility of gold catalysis has been further increased by the discovery of new modes of activation based on the redox chemistry of gold (Au I /Au III ). [4] Right from the beginning, the activation of the triple bond of alkynes has been one of the most successful transformations in gold catalysis.…”

Section: Introduction and Pioneering Workmentioning

confidence: 99%

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Gold‐Catalyzed Alkynylation: Acetylene‐Transfer instead of Functionalization

Brand¹,

Li²,

Waser³

2013

Israel Journal of Chemistry

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Abstract:In the last fifteen years, gold has raised from the status of an inert noble metal to one of the most often used catalyst in synthetic chemistry. The functionalization of the triple bond of alkynes has been especially successful in this respect. In contrast, gold-catalyzed alkynylation methods have begun to emerge only in 2007. Since then, three different approaches have been successful. Gold nanoparticles allowed catalytic cycles based on oxidative arylation on aryl halides to give a "palladium-free Sonogashira reaction". The use of benziodoxol(on)e hypervalent iodine compounds as oxidative alkynylation reagents had then allowed the C-H functionalization of electron-rich heterocycles under mild conditions and with a very broad functional group tolerance. Finally, the use of iodobenzene acetate or Selectfluor as external oxidant led to the first alkynylation methods based on direct C-H/C-H coupling. In only six years, gold-catalyzed alkynylation methods have raised from nonexistent to useful synthetic protocols for the synthesis of structurally diverse alkynes. When considering that acetylenes are among the most important building blocks for applications in synthetic chemistry, chemical biology and materials science, a tremendous potential for further development of gold-catalyzed alkynylation can be expected for the future.

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Section: Methodsmentioning

confidence: 96%

Section: Introduction and Pioneering Workmentioning

confidence: 99%

Gold‐Catalyzed Alkynylation: Acetylene‐Transfer instead of Functionalization

Brand¹,

Li²,

Waser³

2013

Israel Journal of Chemistry

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“…A plethora of gold(I) complexes and enyne substrates have been employed to access a variety of products with increased molecular complexity under very mild reaction conditions. [1][2][3][4][5][6] The mechanism is presumed to proceed via initial coordination of the gold(I) moiety to the alkyne which enhances its electrophilicity allowing for subsequent nucleophilic attack from the alkene. [7][8] However, low temperature NMR spectroscopy investigations indicated no preference between alkyne and alkene coordination, suggesting that the procedure may be kinetically rather than thermodynamically controlled.…”

Section: Introductionmentioning

confidence: 99%

A simple Ag(I)-enyne cation

Sanguramath

Townsend

Russell

2016

Journal of Organometallic Chemistry

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General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. 9190401, Israel AbstractA simple cationic Ag(I)-1,3-enyne complex was synthesized and characterized. In the solid state, single crystal X-ray crystallography showed the Ag(I) centre bonded in an asymmetric manner exclusively to the alkyne portion of the substrate. NMR spectroscopy studies showed this structure is maintained in solution over the temperature range of -90 to +60 °C.

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“…4,[7][8][9][10][11][12][13][14][15][16][17] In this field, gold-catalyzed cycloisomerization reactions of poly-unsaturated substrates received the attention of many research groups in the last few years. [18][19][20] Recently, a straightforward access to polyconjugated Gold catalyst Scheme 1. Access to conjugated bis-enones via gold catalysis…”

Section: Introductionmentioning

confidence: 99%