A New Insight into Gold(I)‐Catalyzed Hydration of Alkynes: Proton Transfer

Krauter, Caroline M.; Hashmi, A. Stephen K.; Pernpointner, Markus

doi:10.1002/cctc.201000136

Cited by 199 publications

(124 citation statements)

References 25 publications

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“…However, later studies have clearly shown that intermediate 66 is an artifact of the gas phase and that is quite unlikely in the liquid phase. [96] Moreover, later experimental work has demonstrated that the attack of oxygen [97a-98] and carbon [97b] nucleophiles on the gold-alkyne intermediate occurs preferentially through the opposite face of coordination (anti). In any case, the work by Teles and co-workers opened the door toward gold-catalyzed hydroadditons to alkynes and many of their assumptions are still accepted.…”

Section: A Corma and A Leyva-pørezmentioning

confidence: 99%

Similarities and Differences between the “Relativistic” Triad Gold, Platinum, and Mercury in Catalysis

2011

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Relativistic effects in the valence shell of the elements reach a maximum in the triad Pt-Au-Hg and determine their catalytic activity in organic reactions. In this Review we examine the catalytic activity of Pt, Au, and Hg compounds for some representative reactions, and discuss the respective benefits and disadvantages along with other relevant properties, such as toxicity, price, and availability. For the reactions considered, gold catalysts are generally more active than mercury or platinum catalysts.

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Section: A Corma and A Leyva-pørezmentioning

confidence: 99%

Similarities and Differences between the “Relativistic” Triad Gold, Platinum, and Mercury in Catalysis

2011

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“…The final step corresponds to the dissociation of [Au(IPr)] + from the enol ether intermediate VI to deliver the transhydroalkoxylated product, 73 with a free energy change of -13.7 kcal/mol, overcoming a relatively high energy barrier of 15.2 kcal/mol via a phenol-assisted pathway, even though this protonation step might be assisted by an acid reagent. 74,75 However, it is also possible that this last step is assisted by the alkyne substrate, being just 6.4 kcal/mol higher in energy than the water-assisted pathway, 76 thus releasing the vinyl ether and regenerating complex I. Given that I and [Au(IPr)(OHR)] + are close in energy, they will be in equilibrium under the reaction conditions.…”

Section: Digold Catalysismentioning

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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“…[38] Thec alculations were performed at DFT level using 6-31G**b asis set for all atoms exceptg oldf or which SDD basis was used. We positioned andc haracterized each transitions tate (TS) using as can procedure leading to ah igh energy structure which was furthermore freely optimized (Supporting Information).…”

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confidence: 99%

Water‐Soluble Gold–N‐Heterocyclic Carbene Complexes for the Catalytic Homogeneous Acid‐ and Silver‐Free Hydration of Hydrophilic Alkynes

et al. 2015

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A New Insight into Gold(I)‐Catalyzed Hydration of Alkynes: Proton Transfer

Cited by 199 publications

References 25 publications

Similarities and Differences between the “Relativistic” Triad Gold, Platinum, and Mercury in Catalysis

Similarities and Differences between the “Relativistic” Triad Gold, Platinum, and Mercury in Catalysis

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

Water‐Soluble Gold–N‐Heterocyclic Carbene Complexes for the Catalytic Homogeneous Acid‐ and Silver‐Free Hydration of Hydrophilic Alkynes

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