Gold(I)‐Catalyzed Reactions of Propargyl Esters with Vinyl Derivatives

Sperger, Christian A.; Tungen, Jørn Eivind; Fiksdahl, Anne

doi:10.1002/ejoc.201100291

Cited by 52 publications

(30 citation statements)

References 26 publications

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“…The mechanistic studies showedt hat the intramolecular CÀOb ond formation proceeded through au nique carboxy migration from an Au III organogold intermediate. [163][164][165][166][167] The CÀOc oupling product is formed through selectfluor-mediated fluorination/defluorinations equences.H owever,t he revised role of selectfluor proposed from the theoretical calculations is yet to be verified by experimental studies. [162] Contrary to the originally proposed mechanisms, calculations indicated that selectfluor does not oxidize Au I to Au III .…”

Section: Selectfluor As Asacrificial Oxidantina U I /Au Iii Catalysismentioning

confidence: 99%

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Nijamudheen

Datta

2019

Chemistry A European J

153

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Transition-metal-catalyzed cross-couplingr eactions are central to many organic synthesis methodologies. Traditionally,P d, Ni, Cu, and Fe catalysts are used to promote these reactions. Recently,m any studies have showedt hat both homogeneous and heterogeneous Au catalysts can be used for activating selective cross-coupling reactions.H ere, an overview of the past studies, current trends, andf uture directions in the field of gold-catalyzed coupling reactions is presented.D esign strategiest oa ccomplish selective homocoupling and cross-coupling reactions under both homogeneous and heterogeneous conditions, computational and ex-perimental mechanistic studies, and their applicationsi nd iverse fields are critically reviewed. Specific topics covered are:o xidant-assisted and oxidant-free reactions;s train-assisted reactions;d ual Au and photoredoxc atalysis;b imetallic synergistic reactions;m echanismso fr eductivee limination processes;e nzyme-mimicking Au chemistry;c lustera nd surface reactions;a nd plasmonic catalysis. In the relevant sections, theoretical and computational studies of Au I /Au III chemistry are discussed and the predictionsf rom the calculationsa re compared with the experimental observations to derive useful design strategies.A. Nijamudheen earnedh is PhD from IACS, Kolkata,i n2 015. Currently,h ei sapostdoctoral researcher atF loridaS tate University.H is researchi nterests are in computational catalysis, solar energym aterials, and beyond Li-ion battery technologies.Ayan Dattai sc urrently aP rofessor at IACS, Kolkata.H is research interests include theoretical and computational studieso ft ransitionmetal-catalyzed reactions,o pto-electronic properties of organic and solid-statem aterials, and the design of renewableenergymaterials. He has won several awards including the DST-SERB Distinguished Investigator Award (DIA) in 2019.

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Section: Selectfluor As Asacrificial Oxidantina U I /Au Iii Catalysismentioning

confidence: 99%

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Nijamudheen

Datta

2019

Chemistry A European J

153

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“…From the results of this and previous studies on goldcatalyzed reactions between propargyl esters and enol ether or enol esters, 11,15 product distribution depends mainly on the structure of the enols. Enol ethers may lead to formal [3+2] cycloaddition products, but enol esters produce primarily cyclopropanation products.…”

Section: Introductionmentioning

confidence: 90%

“…A similar cyclopropanation of vinyl esters has been reported by Fiksdahl, but the substrate was much simpler and a different Au catalyst was used. 15 In the presence of gold catalyst 2, propargyl ester 1 and vinyl ester 4 reacted smoothly at room temperature to afford the vinyl cyclopropane 7 in 75% yield, Scheme 3.…”

Section: Introductionmentioning

confidence: 99%

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Gold catalysis: up to six new bonds by a domino [3+2]/[2+1]/[2+1] cycloaddition

Conyers

Barnes

Gung

2015

Tetrahedron Letters

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a b s t r a c tIn the presence of the N-heterocyclic carbene gold catalyst (IPrAuNCPhSbF 6 , 2), propargyl ester 1 undergoes a formal [3+2] cycloaddition reaction with vinyl ethers at room temperature. If the reaction was allowed to continue with excess propargyl ester, one or two sequential cyclopropanations occur on the enolate double bond of the [3+2] reaction product. The one-pot domino cycloaddition reactions created cyclopropanation products with multiple rings, formed multiple new sigma bonds, and new stereocenters. When 2-methoxypropene was allowed to react with excess propargyl ester 1 in the presence of the Au(I) catalyst 2, two tandem cyclopropanations occurred on the initial [3+2] cycloaddition product, which yields a product with a tricyclic carbon frame, six new sigma bonds, and eight new stereocenters. Hence the observation sets a new record for gold-catalyzed domino reactions. The assignment of the product stereochemistry was performed by NMR spectroscopy and confirmed by an X-ray structure analysis.

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“…46 Most vinyl derivatives afforded the cyclopropanation products. In one case, both cyclopropane and cyclopentene products were observed and the cyclopropane could not be converted to the corresponding cyclopentene.…”

Section: Cycloadditions Involving Au-catalyzed 12-acyloxy Migratimentioning

confidence: 99%

Rhodium-catalyzed acyloxy migration of propargylic esters in cycloadditions, inspiration from the recent “gold rush”

et al. 2012

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Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative addition, migratory insertion, and reductive elimination may lead to ample new opportunities for the design of new reactions. This tutorial review summarizes recent developments in Rh-catalyzed 1,3- and 1,2-acyloxy migration of propargylic esters in a number of cycloaddition reactions. Related Au- and Pt-catalyzed cycloadditions involving acyloxy migration are also discussed.

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Gold(I)‐Catalyzed Reactions of Propargyl Esters with Vinyl Derivatives

Abstract: A gold-catalyzed olefin cyclopropanation reaction of propargyl esters with vinyl ester or vinyl sulfonamide derivatives was investigated for the synthesis of highly substituted cyclo-

Cited by 52 publications

References 26 publications

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Gold catalysis: up to six new bonds by a domino [3+2]/[2+1]/[2+1] cycloaddition

Rhodium-catalyzed acyloxy migration of propargylic esters in cycloadditions, inspiration from the recent “gold rush”

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