Highly Efficient Gold(I)-Catalyzed Regio- and Stereoselective Hydrocarboxylation of Internal Alkynes

Dupuy, Stéphanie; Gasperini, Danila; Nolan, Steven P.

doi:10.1021/acscatal.5b02090

Cited by 69 publications

(43 citation statements)

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“…As a possible rationale for the results obtained, based on previous literature suggestions, a mechanism can be proposed for the cyclisation of alkynoic acids (Scheme ) ,,. Dissociation of pre‐catalyst 1a , [{Au(IPr)} 2 (μ‐OH)][BF 4 ], into 1b , [Au(IPr)(OH)], and 1b′ , [Au(IPr)][BF 4 ], can be considered the first step.…”

Section: Figurementioning

confidence: 80%

Gold(I)‐Catalysed Cyclisation of Alkynoic Acids: Towards an Efficient and Eco‐Friendly Synthesis of γ‐, δ‐ and ϵ‐Lactones

et al. 2016

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Thei mproved synthesis of g-, d-a nd elactones using ad inuclear N-heterocyclic carbene (NHC)-gold(I) catalyst is reported. This solventfree process provides access to g-a nd d-lactones in high regio-and stereoselectivity.R eactions were performed at low catalyst loadings andw ithout the need for any additives.T he use of adigold pre-catalyst providesanew synthetic route to functionalised e-lactones,p oorly accessible using previous methodologies.

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Section: Figurementioning

confidence: 80%

Gold(I)‐Catalysed Cyclisation of Alkynoic Acids: Towards an Efficient and Eco‐Friendly Synthesis of γ‐, δ‐ and ϵ‐Lactones

et al. 2016

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“…27 and 28 in Figure 2, for the hydrocarboxylation of alkynes has been described. 95,96 The former, developed by Zhang and co-workers, 95 was able, in combination with NaBArF, to promote the addition of benzoic acid to the internal alkynes n PentC≡C n Pent, PhC≡CCO2Et and MeC≡CCH2CH2OBn in fluorobenzene at 80 °C. The reactions, performed with very low metal loadings (0.015-0.15 mol%), led to the expected anti-addition products in very high yields (85%-99%) after 15-20 h. Concerning the regioselectivity of the process, starting from PhC≡CCO2Et the addition of the benzoate group took place exclusively on the Ph-Csp carbon, while in the case of MeC≡CCH2CH2OBn a mixture of regioisomers was obtained.…”

Section: Scheme 12mentioning

confidence: 99%

“…Remarkably, DFT calculations supported the role of the amide group of the biaryl-phosphine ligand in directing the attack of the carboxylic acid to the π-coordinated C≡C bond via hydrogen bonding. For its side, the digold hydroxide complex 28, developed by Nolan and co-workers, 96 showed a very high activity and wide scope under solvent-and silver-free conditions. Both activated and unactivated internal alkynes could be hydro-oxycarbonylated with a large variety of carboxylic acids (aromatic, heteroaromatic, aliphatic, α,β-unsaturated and even with formic acid) using 0.5 mol% of this complex at 80 °C, leading to the corresponding (Z)-enol esters in high yields (anti addition).…”

Section: Scheme 12mentioning

confidence: 99%

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

González-Liste¹,

Francos²,

García‐Garrido³

et al. 2017

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The intermolecular addition of carboxylic acids to alkynes is one of the most straightforward and atomeconomical methods currently available for the preparation of synthetically useful enol esters. However, the vast majority of works have focused on the use of terminal alkynes, substrates much more reactive than their corresponding internal counterparts. In fact, efficient and general protocols for hydro-oxycarbonylation of internal alkynes have only seen the light in recent years. In the present review article an overview of the progress made in the field is given. Catalytic reactions promoted by ruthenium, palladium, silver and gold complexes/salts, along with some specific metal-free protocols, are covered.

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“…13,14 Well-defined digold pre-catalysts are now used for a number of applications. [15][16][17][18][19][20][21][22][23] Dual gold catalysis might help to overcome the hurdle that Au I has only two coordination sites available, with a linear geometry. 24 Another issue that remains is that understanding how ligand structure affects reactivity in catalysis, although some useful empirical observations have been made.…”

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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Highly Efficient Gold(I)-Catalyzed Regio- and Stereoselective Hydrocarboxylation of Internal Alkynes

Cited by 69 publications

References 56 publications

Gold(I)‐Catalysed Cyclisation of Alkynoic Acids: Towards an Efficient and Eco‐Friendly Synthesis of γ‐, δ‐ and ϵ‐Lactones

Gold(I)‐Catalysed Cyclisation of Alkynoic Acids: Towards an Efficient and Eco‐Friendly Synthesis of γ‐, δ‐ and ϵ‐Lactones

The intermolecular hydro-oxycarbonylation of internal alkynes: current state of the art

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

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