Intramolecular Cyclizations of Enynes Using RuClH(CO)(PPh<sub>3</sub>)<sub>3</sub>

Nishida, Motohiro; Adachi, Naoko; Onozuka, Kiyoko; Matsumura, Hiroshi; Mori, Miwako

doi:10.1021/jo981715b

Cited by 66 publications

(42 citation statements)

References 14 publications

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“…[54] Katz and Sivavec discovered the reaction by using tungsten, but then tested it with several transition metals. [55] Its application in total synthesis is quite recent and well-exemplified in a recent review by Nicolaou et al [56] Various catalysts including the dimer [{RuCl 2 (CO) 3 } 2 ], [57] the Grubbs catalyst, [58] Reactions may also be initiated by hydrometalation to give functionalized 1,3-dienes, [61] as hydroruthenation of the triple bond is followed by a 5-exo-trig cyclization and then a b elimination. (44)].…”

Section: Ru-catalyzed Cycloisomerization Reactionsmentioning

confidence: 99%

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

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

951

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: Ru-catalyzed Cycloisomerization Reactionsmentioning

confidence: 99%

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

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

951

248

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“…So wurde für die Bildung des Cycloheptens 133 aus 132 [Gl. (42)] der in Schema 15 [60] Reaktionen unter Hydrometallierung führen zur Bildung funktionalisierter 1,3-Diene, [61] weil auf die Hydroruthenierung der Dreifachbindung eine 5-exo-trig-Cyclisierung und eine b-Eliminierung folgen. Beispielsweise cyclisierte der a,b-ungesättigte (45)].…”

Section: Ru-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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“…NH 4 Cl (aq) ( 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2H), 2.13-2.08 (m, 2H), 1.47-1.23 (m, 8H), 0.89 (t, J = 6.6 Hz, 3H), 0. 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 …”

Section: Acs Paragon Plus Environmentunclassified

“…Mori and co-workers have observed similar reactivity of enynes in the presence of ruthenium hydrides. 16 An improved procedure for the formation of dienes B has recently been reported which relies on ruthenium complex Cp*RuCl(COD) and is compatible with both aryl-and alkyl-substituted alkynes. 15 Our main goal for this study was to improve the ethylene insertion process and to expand our repertoire of alkynes to include alkyl substituted substrates.…”

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confidence: 99%

Ruthenium Hydride Catalyzed Silylvinylation of Internal Alkynes Using Ethylene as an Additive

et al. 2015

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An efficient synthetic strategy for the regiospecific silylvinylation of internal alkynes is described. This transformation is catalyzed by RuHCl(CO)(SIMes)PPh3 and provides a net 5-exo-dig trans-silylvinylation of internal alkynes. Ethylene was used to decrease reaction times and displayed altered selectivity at increased pressure. Furthermore, alkyl-substituted alkynes were acceptable substrates at 80 psi of ethylene.

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Intramolecular Cyclizations of Enynes Using RuClH(CO)(PPh₃)₃

Cited by 66 publications

References 14 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

Ruthenium Hydride Catalyzed Silylvinylation of Internal Alkynes Using Ethylene as an Additive

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Intramolecular Cyclizations of Enynes Using RuClH(CO)(PPh3)3

Cited by 66 publications

References 14 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

Ruthenium Hydride Catalyzed Silylvinylation of Internal Alkynes Using Ethylene as an Additive

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Intramolecular Cyclizations of Enynes Using RuClH(CO)(PPh₃)₃