Tracking gold acetylides in gold(i)-catalyzed cycloisomerization reactions of enynes

Simonneau, Antoine; Jaroschik, Florian; Lesage, Denis; Karanik, Magdalena; Guillot, Régis; Malacrìa, Max; Tabet, Jean‐Claude; Goddard, Jean‐Philippe; Fensterbank, Louis; Gandon, Vincent; Gimbert, Yves

doi:10.1039/c1sc00478f

Cited by 95 publications

(40 citation statements)

References 39 publications

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“…13,[26][27][28][29][30][31][32][33] Complexes in the frames can be detected by ESI-MS. 13 The symbol (LAu + )* is used for an active form of the catalyst.…”

Section: Methodsmentioning

confidence: 99%

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

et al. 2015

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A new method to investigate the reaction kinetics of intermediates in solution by electrospray ionization mass spectrometry is presented. The method, referred to as delayed reactant labeling, allows investigation of a reaction mixture containing isotopically labeled and unlabeled reactants with different reaction times. It is shown that we can extract rate constants for the degradation of reaction intermediates and investigate the effects of various reaction conditions on their half-life. This method directly addresses the problem of the relevance of detected gaseous ions toward the investigated reaction solution. It is demonstrated for geminally diaurated intermediates formed in the gold mediated addition of methanol to alkynes. Delayed reactant labeling allows us to directly link the kinetics of the diaurated intermediates with the overall reaction kinetics determined by NMR spectroscopy. It is shown that the kinetics of protodeauration of these intermediates mirrors the kinetics of the addition of methanol demonstrating they are directly involved in the catalytic cycle. Formation as well as decomposition of diaurated intermediates can be drastically slowed down by employing bulky ancillary ligands at the gold catalyst; the catalytic cycle then proceeds via monoaurated intermediates. The reaction is investigated for 1-phenylpropyne (Ph-CC-CH3) using [AuCl(PPh3)]/AgSbF6 and [AuCl(IPr)]/AgSbF6 as model catalysts. Delayed reactant labeling is achieved by using a combination of CH3OH and CD3OH or Ph-CC-CH3 and Ph-CC-CD3.

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“…13,[26][27][28][29][30][31][32][33] Complexes in the frames can be detected by ESI-MS. 13 The symbol (LAu + )* is used for an active form of the catalyst.…”

Section: Methodsmentioning

confidence: 99%

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

et al. 2015

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“…124 Experimental and computational work suggested that these types of σ,π-digold( i ) complexes are unreactive in the cycloisomerization process.…”

Section: Digold Complexesmentioning

confidence: 99%

Intriguing mechanistic labyrinths in gold(i) catalysis

2014

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“…The use of tetraarylborate (BAr F ) as the anion was also found to be important to obtain consistently good yields . Kinetic experiments suggested that the deprotonation of terminal alkynes 132 is slower with this bulky anion, which minimizes the formation of undesired σ,π‐digold(I) alkyne complexes ,…”

Section: Development Of An Enantioselective Intermolecular [2+2] Cyclmentioning

confidence: 99%

“…In the case of substrates bearing terminal alkynes, σ, π‐digold(I) alkyne complexes can also be formed, which are unproductive dead‐ends in catalytic reactions of enynes ,. However, the formation of these dinuclear gold(I) complexes is reversible, and in the presence of protic sources the free alkynes can be regenerated by protonolysis.…”

Section: Introductionmentioning

confidence: 99%

Gold(I)‐Catalysis for the Synthesis of Terpenoids: From Intramolecular Cascades to Intermolecular Cycloadditions

Mayans

Armengol-Relats

Calleja

et al. 2018

Israel Journal of Chemistry

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Gold(I)‐catalyzed cycloisomerizations of 1,n‐enynes proceed through electrophilic intermediates that can be trapped intra‐ or intermolecularly by a variety of hetero‐ and carbon nucleophiles to form complex skeletons in a single step. This review covers the efforts of our group towards the development of new reactions that have been successfully applied in the total synthesis of several natural terpenoids and related carbocyclic structures, as well as for the ready access to challenging linear acenes.

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Tracking gold acetylides in gold(i)-catalyzed cycloisomerization reactions of enynes

Abstract: International audienc

Cited by 95 publications

References 39 publications

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

Intriguing mechanistic labyrinths in gold(i) catalysis

Gold(I)‐Catalysis for the Synthesis of Terpenoids: From Intramolecular Cascades to Intermolecular Cycloadditions

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