Cationic Au(I)-Catalyzed Cycloisomerization of Aromatic Enynes for the Synthesis of Substituted Naphthalenes

Shibata, Takanori; Ueno, Yukihiko; Kanda, Kazumasa

doi:10.1055/s-2006-926261

Cited by 100 publications

(36 citation statements)

References 1 publication

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“…The cyclization of aryl alkyne 469 promoted a selective [4+2] cycloaddition to give 2,3,9,9a-tetrahydro-1H-cyclopenta [b]naphthalene 470 in 86 % yield [Eq. (157)]. [178] Various catalysts were efficient for this transformation, with a (biarylphosphane)gold chloride being the most reactive.…”

Section: Methodsmentioning

confidence: 99%

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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%

“…(134)]. [157] Depending on the substitution pattern of the triple bond, a 5-exo-dig-type cyclization can also proceeded and be competitive to the 6-endo-type cycloisomerization. The benzannulation of enyne 414 gave an 87 % yield of a 7:1 mixture of the naphthalene 415 and the corresponding indene 416.…”

Section: Enyne Rearrangementsmentioning

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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“…[51] Depending on the nature of the alkyne, the cyclization followed either 6-endo or 5-exo manifolds. The alkyl-substituted alkyne 335 afforded naphthalene 336, while the terminal or halogen-substituted alkynes 337 favored the formation of indenes 338…”

Section: Formation Of Naphthalenes and Methyleneindenesmentioning

confidence: 99%

Gold and Platinum Catalysis of Enyne Cycloisomerization

2006

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This account provides a comprehensive overview of the development of gold and platinum catalysis of the enyne cycloisomerization. The use of these soft, alkynophilic metals enables mild, chemoselective and efficient transformations of a variety of readily available acyclic enynes to a wide range of synthetically useful carbocyclic and heterocyclic products. The review is organized according to diverse structural types of enynes that undergo skeletal cycloisomerizations. The account begins with an overview of transformations of primarily 1,6-enynesheptenes. This section is followed by the discussion of cycloisomerizations of 1,5-enynes, which enable a rapid access to a range of other cyclic products, including bicycloA C H T U N G T R E N N U N G [3.1.0]hexenes, cyclohexadienes, heterobicycloalkenes, methylenecyclopentenes, naphthalenes and methyleneindenes. In addition, the [3,3] rearrangement of 1,5-enynes provides efficient access to the corresponding allenes. The account concludes with an overview of the most recent studies on gold-and platinum-catalyzed cycloisomerizations of 1,4-and 1,3-enynes. Due to the rapidly increasing interest in this area during the past three to five years, we believe that this review provides a timely and comprehensive discussion of the development gold-and platinum-catalyzed cycloisomerization starting from the initial pioneering investigations to the latest advances in the field. A significant emphasis is placed on the mechanistic discussion of the observed manifolds of skeletal reorganizations.

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“…(134)]. [157] Abhängig vom Substituenten der Dreifachbindung kann auch eine 5-exo-digCyclisierung stattfinden und mit der 6-endo-Cycloisomerisierung konkurrieren. Die Benzanellierung des Enins 414 ergab entsprechend in 87 % Ausbeute ein 7:1-Gemisch aus dem Naphthalin 415 und dem entsprechenden Inden 416.…”

Section: Au-katalysierte Cycloisomerisierungenunclassified

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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Cationic Au(I)-Catalyzed Cycloisomerization of Aromatic Enynes for the Synthesis of Substituted Naphthalenes

Abstract: A cationic Au(I) complex catalyzed the cycloisomerization of aromatic enynes that possess a substituent on their alkyne terminus. Cyclization of the 6-endo-dig type proceeded dominantly to give 1,3-di-and 1,2,3-trisubstituted naphthalenes.

Cited by 100 publications

References 1 publication

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

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

Gold and Platinum Catalysis of Enyne Cycloisomerization

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

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