Copper-Catalyzed Cycloisomerizations of 5-En-1-yn-3-ols

Fehr, Charles; Farris, Iris; Sommer, Horst

doi:10.1021/ol0603864

Cited by 54 publications

(25 citation statements)

References 7 publications

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“…(185)]. [207] These results are in agreement with a mechanism in which the cyclopropanation precedes the rearrangement. The same research group also described an efficient synthesis of a potential flavor compound (À)-cubebol (556) by a stereoselective cycloisomerization.…”

Section: Cu-catalyzed Cycloisomerizationssupporting

confidence: 80%

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

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

950

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: Cu-catalyzed Cycloisomerizationssupporting

confidence: 80%

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

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

950

248

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“…Indeed, PtCl 2 ‐catalyzed cycloisomerization of 8 a and 8 b (88:12) afforded 9 a and 9 b with a 94:6 selectivity (Table 1, entry 4), and chromatographically enriched 8 a (98 % stereochemical purity) afforded 9 a with excellent facial selectivity (99:1; entry 5). Interestingly, inexpensive [Cu(CH 3 CN) 4 ]BF 4 (2 mol %) also efficiently catalyzed the cycloisomerization (99:1; 77 % isolated yield after 90 % conversion) 9. Prolonged reaction times or higher temperatures (70 °C) favored the formation of byproducts.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of (−)‐Cubebol by Face‐Selective Platinum‐, Gold‐, or Copper‐Catalyzed Cycloisomerization: Evidence of Chirality Transfer and Mechanistic Insights

Fehr

Winter

Magpantay

2009

Chemistry A European J

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We describe in detail a direct, stereoselective synthesis of (-)-cubebol based on a Pt-, Au-, or Cu-catalyzed cycloisomerization in which control of the configuration of the propargylic center is essential for the facial selectivity. In addition, we show that cycloisomerization reactions of enantioenriched propargyl pivalates occur with substantial chirality transfer. We confirm a mechanism by means of cyclization followed by an [1,2]-acyl migration for the Pt- and the Au-catalyzed cycloisomerization. So far, no evidence supports that the Cu-catalyzed cycloisomerization follows the same reaction course.

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“…(185)]. [207] Diese Ergebnisse sind in Einklang mit einem Mechanismus, in dem die Cyclopropanierung der Umlagerung vorausgeht. Dieselbe Arbeitsgruppe beschrieb auch eine leistungsfähige Synthese des potenziellen Aromastoffs (À)-Cubebol (556) über eine stereoselektive Cycloisomerisierung.…”

Section: Cu-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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Copper-Catalyzed Cycloisomerizations of 5-En-1-yn-3-ols

Cited by 54 publications

References 7 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

Synthesis of (−)‐Cubebol by Face‐Selective Platinum‐, Gold‐, or Copper‐Catalyzed Cycloisomerization: Evidence of Chirality Transfer and Mechanistic Insights

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

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