Intramolecular [4 + 2] Cycloadditions of 1,3-Enynes or Arylalkynes with Alkenes with Highly Reactive Cationic Phosphine Au(I) Complexes

Nieto‐Oberhuber, Cristina; López, Susana Torío; Echavarren, Antonio M.

doi:10.1021/ja042257t

Cited by 537 publications

(298 citation statements)

References 22 publications

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“…In 1998 we introduced a new class of air-stable [1] phosphine ligands based on the dialkylbiaryl phosphine backbone. [2] These phosphines have been used as ligands for gold, [3][4][5][6][7][8][9][10][11] silver, [12] rhodium, [13,14] ruthenium [15][16][17] and copper [18] where they have been shown to impart improvements in reactivity and catalyst stability. It is in reactions catalyzed by palladium, however, that they have had by far the greatest impact including the Sonogashira, [19] Negishi, [20] Hiyama, [21][22][23] Kumada [24] and Suzuki [25][26][27][28][29][30] cross-coupling reactions, Heck reaction, [31][32][33] enolate arylation [34][35][36][37] and allylation, [38] reductive cyclization [39] and etherification, [40][41][42][43] silylation, [44] borylation, [45]…”

Section: Introductionmentioning

confidence: 99%

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

2008

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Palladium-catalyzed amination of aryl halides has undergone rapid development in the last 12 years. This has been largely driven by implementation of new classes of ligands. Biaryl phosphines have proven to provide especially active catalysts in this context. This review discusses the applications that these catalysts have found in C-N cross-coupling in heterocycle synthesis, pharmaceuticals, materials science and natural product synthesis.

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Section: Introductionmentioning

confidence: 99%

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

2008

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“…1,2,3 These reactions involving Rh, Pd, or Pt are generally postulated to proceed via metallacyclopentene intermediates, inherently involving an increase in the formal oxidation state of the metal. 1,4 On the other hand, gold(I)-catalyzed enyne 5 and some related 1,6-allenyne cycloisomerization reactions 6 are proposed to proceed without a change in the formal oxidation state of the catalyst. 7 We report a combined experimental and computational investigation of gold(I) catalysis of an allenyne cyclization that proceeds via a unique mechanism involving cationic phosphinegold(I) activation of an in situ generated phosphinegold(I) acetylide.…”

Section: Introductionmentioning

confidence: 99%

Gold-Catalyzed Cycloisomerization of 1,5-Allenynes via Dual Activation of an Ene Reaction

et al. 2008

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A tris-triphenylphosphinegold oxonium tetrafluoroborate, [(Ph 3 PAu) 3 O]BF 4 , catalyzes the rearrangement of 1,5-allenynes to produce cross-conjugated trienes. Experimental and computational evidence shows that the ene reaction proceeds through a unique nucleophilic addition of an allene double bond to a cationic phosphinegold(I) complexed phosphinegold(I) acetylide, followed by a 1,5-hydrogen shift.

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“…25 The coordination of phosphines to the gold centre stabilise it and allows for improved reactivity. 26 NHC ligands provide an alternative steric profile, 27 and allow for different levels of σ-donation and π-backbonding, [28][29][30][31][32][33] which modifies the interactions of the gold complex with substrates that are bound trans-to the NHC. The highest catalytic turnover numbers (TONs) were obtained by Hashmi and coworkers.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2017

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This version is available at https://strathprints.strath.ac.uk/61289/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the Strathprints administrator: strathprints@strath.ac.ukThe Strathprints institutional repository (https://strathprints.strath.ac.uk) is a digital archive of University of Strathclyde research outputs. It has been developed to disseminate open access research outputs, expose data about those outputs, and enable the management and persistent access to Strathclyde's intellectual output. Herein we study the hydroalkoxylation and hydrophenoxylation of alkynes using density functional theory calculations, and compare two possible mechanisms that have been proposed previously on the basis of theoretical and experimental studies, which unravel different preferences because of both the nature of the alkyne and alcohol, as well as the non-innocent role of the counter-anion of the dual gold based catalyst. Entropy is found to have a significant effect, rendering the nucleophilic attack of the monoaurated intermediate [Au(L)(η 2 -alkyne)] + difficult both kinetically and thermodynamically; this mechanism cannot easily form only the trans-alkene product that is observed experimentally. Instead, reaction via a dual gold catalysed mechanism presents much lower barriers. In addition, for the sake of direct comparison with recent results by Belanzoni, Zuccaccia, oversimplification of the Nheterocyclic carbene (NHC) ligand in the calculations might decrease the enthalpy barrier and lead to results that are not directly applicable to experiment. Moreover, the alkylic or arylic nature of the alkyne and/or alcohol is also tested. ORGANIC & BIOMOLECULAR CHEMISTRY ARTICLE

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Intramolecular [4 + 2] Cycloadditions of 1,3-Enynes or Arylalkynes with Alkenes with Highly Reactive Cationic Phosphine Au(I) Complexes

Cited by 537 publications

References 22 publications

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

Gold-Catalyzed Cycloisomerization of 1,5-Allenynes via Dual Activation of an Ene Reaction

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

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