Gold(<scp>i</scp>)-catalysed arylation of 1,6-enynes: different site reactivity of cyclopropyl gold carbenes

Amijs, Catelijne H. M.; Ferrer, Catalina; Echavarren, Antonio M.

doi:10.1039/b615335f

Cited by 154 publications

(79 citation statements)

References 36 publications

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“…The research group of Echavarren observed independently a similar reactivity of 1,6-enynes. [180] It is interesting to note that the reactivity of the presumed gold carbene intermediate 457 [see Scheme 36 and Eqs. (149) and (150) Polycyclic heterocycles bearing an oxygen bridge were obtained by a tandem cyclization/Prins reaction.…”

Section: Methodsmentioning

confidence: 99%

Cycloisomerization of 1,n‐Enynes: Challenging Metal‐Catalyzed Rearrangements and Mechanistic Insights

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

937

248

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Metal-catalyzed cycloisomerization reactions of 1,n-enynes have appeared as conceptually and chemically highly attractive processes as they contribute to the highly demanded search for atom economy and allow the discovery of new reactions. Since the pioneering studies with palladium by the research group of Barry Trost in the mid-1980s, several other metals have been identified as excellent catalysts for the rearrangement of enyne skeletons. Moreover, the behavior of 1,n-enynes may be influenced by other functional groups such as alcohols, aldehydes, ethers, alkenes, or alkynes, thus enhancing the molecular complexity of the synthesized products. Apart from the intrinsic rearrangements of 1,n-enynes, several tandem reactions incorporating intramolecular trapping agents or intermolecular partners have been discovered. This Review aims to highlight the main contributions in this field of catalysis and to propose and comment on the mechanistic insights of the recent discoveries.

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Section: Methodsmentioning

confidence: 99%

Cycloisomerization of 1,n‐Enynes: Challenging Metal‐Catalyzed Rearrangements and Mechanistic Insights

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

937

248

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“…(180)]. [203] Der Mechanismus dieser Tandemreaktion wurde bisher noch nicht untersucht; sie verläuft vermutlich aber über ein Metallacyclopenten (ähnlich zu 530, Schema 41 [205] Die Cycloaddition von 544 beispielsweise verlief glatt und führte zum funktionalisierten Siebenringderivat 545 [Gl.…”

Section: Enin-tandemreaktionenunclassified

Cycloisomerisierungen von 1,n‐Eninen: faszinierende metallkatalysierte Umlagerungen und mechanistische Einblicke

2008

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Metallkatalysierte Cycloisomerisierungen von 1,n‐Eninen haben sich als konzeptionell und chemisch höchst attraktive Reaktionen erwiesen, da sie dem häufig geforderten Streben nach Atomökonomie nachkommen und neuartige Reaktionsverläufe ermöglichen. Seit den bahnbrechenden Arbeiten in der Gruppe von Barry Trost mit Palladium Mitte der 1980er Jahre wurden viele weitere Metalle als hervorragende Katalysatoren für Enin‐Gerüstumlagerungen identifiziert. Zudem kann das Verhalten von 1,n‐Eninen durch funktionelle Gruppen wie Alkohol‐, Aldehyd‐, Ether‐, Alken‐ oder Alkineinheiten beeinflusst werden, wodurch die Komplexität der synthetisierten Verbindungen zunimmt. Neben den eigentlichen 1,n‐Enin‐Umlagerungen wurden mehrere Tandemreaktionen entdeckt, die intramolekulare Abfangreagentien oder intermolekulare Partner einbeziehen. Diese Übersicht will die wichtigsten Beiträge auf diesem Gebiet der Katalyse behandeln und die mechanistischen Erkenntnisse zu den neuesten Entdeckungen darlegen und kommentieren.

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“…[11][12][13] Recently, the Au I -catalyzed additions of carbon nucleophiles to 1,6-enynes via intermediates 3 have been described. [14,15] A few unsubstituted 1,6-enynes (1, RЈ = H), as well as those bearing alkyl or aryl substituents at the alkyne, can cyclize by endo pathways via intermediates 6 (Scheme 1) to give bicyclic compounds 7. [11,16,17,18] We have found recently that opening of gold(I) intermediates 6 to form seven-membered ring products is also possible.…”

Section: Introductionmentioning

confidence: 99%

On the Mechanism of the Puzzling “Endocyclic” Skeletal Rearrangement of 1,6‐Enynes

et al. 2007

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Skeletal rearrangements of simple 1,6-enynes have been studied in order to determine the factors that control the formation of five-or six-membered rings. Simple 1,6-enynes substituted only at C-4 preferentially give six-membered rings on skeletal rearrangement in the presence of gold(I) catalysts, whereas increasing electron-withdrawing character of substituents at C-4 leads to five-membered rings. Reactions of these simple enynes in the presence of PtCl 4 as catalyst give exclusively exo-double skeletal rearrangements. Enynes substituted at the alkyne also react with Au I catalysts to give exclusively products of exo-double rearrangement.

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Gold(i)-catalysed arylation of 1,6-enynes: different site reactivity of cyclopropyl gold carbenes

Abstract: Gold(I)-catalysed addition of electron-rich arenes and heteroarenes to 1,6-enynes gives two different types of products by reaction of the intermediate cyclopropyl gold carbenes at the cyclopropane or at the carbene.

Cited by 154 publications

References 36 publications

Cycloisomerization of 1,n‐Enynes: Challenging Metal‐Catalyzed Rearrangements and Mechanistic Insights

Cycloisomerization of 1,n‐Enynes: Challenging Metal‐Catalyzed Rearrangements and Mechanistic Insights

Cycloisomerisierungen von 1,n‐Eninen: faszinierende metallkatalysierte Umlagerungen und mechanistische Einblicke

On the Mechanism of the Puzzling “Endocyclic” Skeletal Rearrangement of 1,6‐Enynes

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