Gold(I)-Catalyzed Addition of Carboxylic Acids to Alkynes

Chary, Bathoju Chandra; Kim, Sunggak

doi:10.1021/jo101543q

Cited by 85 publications

(59 citation statements)

References 44 publications

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“…This transformation has been previously realized using 5 mol % Ph 3 PAuCl/AgPF 6 with catalyst TONs up to 18(34), and the best catalyst TON (i.e., 124) of this type of reaction was achieved via Ru catalysis. (35) Importantly, the alkenyl esters products possess mildly activated acyl groups and are versatile substrates of broad synthetic utilities.…”

Section: Resultsmentioning

confidence: 94%

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

Wang

et al. 2014

Nat Commun

138

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Most homogenous gold catalyses demand ≥0.5 mol % catalyst loading. Due to the high cost of gold, these reactions are unlikely to be applicable in medium or large scale applications. Here we disclose a novel ligand design based on the privileged biphenyl-2-phosphine framework that offers a potentially general approach to dramatically lowering catalyst loading. In this design, an amide group at the 3’ position of the ligand framework directs and promotes nucleophilic attack at the ligand gold complex-activated alkyne, which is unprecedented in homogeneous gold catalysis considering the spatial challenge of using ligand to reach antiapproaching nucleophile in a linear P-Au-alkyne centroid structure. With such a ligand, the gold(I) complex becomes highly efficient in catalyzing acid addition to alkynes, with a turnover number up to 99,000. Density functional theory calculations support the role of the amide moiety in directing the attack of carboxylic acid via hydrogen bonding.

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Section: Resultsmentioning

confidence: 94%

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

Wang

et al. 2014

Nat Commun

138

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“…A more general study was published by Chary and Kim in 2010 employing the catalytic system [AuCl(PPh3)]/AgPF6 (5 mol%). 88 Thus, they found that, in toluene at 60-110 °C, the in situ formed [Au(PPh3)] + cation cleanly and efficiently catalyzes the anti-addition of different carboxylic acids to both terminal and internal alkynes. With regard to the latter, the results obtained in the four reactions covered by Chary and Kim are shown in Scheme 12.…”

Section: Gold-based Catalystsmentioning

confidence: 99%

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

González-Liste¹,

Francos²,

García‐Garrido³

et al. 2017

Arkivoc

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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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“…No general protocol for vinyl ether synthesis using gold has been reported to date [17]. Nevertheless, there have been examples regarding the intermolecular addition of carboxylic acids [19–20], phenols [21–22] as well as phosphoric acids [23–25] to alkynes. In this context, we report a gold(I)-catalyzed O-vinylation of 1,3-diketones with unactivated alkynes at ambient temperature.…”

Section: Introductionmentioning

confidence: 99%

Ambient gold-catalyzed O-vinylation of cyclic 1,3-diketone: A vinyl ether synthesis

Xi¹,

Dong²,

Shi³

2013

Beilstein J. Org. Chem.

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Gold(I)-Catalyzed Addition of Carboxylic Acids to Alkynes

Abstract: Au(I)-catalyzed hydroacyloxylation of alkynes with carboxylic acids is described. PPh3AuCl/AgPF6 catalyst affords the Markonikov addition products, whereas PPh3AuCl/AgOTf catalyst gives the more stable isomerized products via the Markonikov products.

Cited by 85 publications

References 44 publications

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes

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

Ambient gold-catalyzed O-vinylation of cyclic 1,3-diketone: A vinyl ether synthesis

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