Functionalized carbo- and heterocycles via Pt-catalyzed asymmetric alkoxycyclization of 1,6-enynes

Charruault, Lise; Michelet, Véronique; Taras, Rossana; Gladiali, Serafino; Genêt, Jean‐Pierre

doi:10.1039/b400908h

Cited by 111 publications

(48 citation statements)

References 28 publications

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“…In an enantioselective version of this transformation, [139] a dicationic platinum complex prepared from PtCl 2 , (R)-binepine ((R)-351), and AgSbF 6 catalyzed the reaction of enyne 352 to alcohol 353 in dioxane/H 2 O; the product was obtained in 94 % yield and 85 % ee [Eq. (116)].…”

Section: Angewandte Chemiementioning

confidence: 99%

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

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

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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: Angewandte Chemiementioning

confidence: 99%

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

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

Self Cite

937

248

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“…Die Arbeitsgruppe von Malacria und Fensterbank entwickelte eine nützliche Methode zur Synthese polycyclischer Derivate ausgehend von einfachen 5-Acetoxy-1,3-eninen mit einer C-C-Doppelbindung in der Seitenkette [Gl. (139)]. [165] Sie gingen von einer klassischen 3,3-Umlagerung in Gegenwart des [AuCl-(PPh 3 )] /AgSbF 6 -Katalysators aus, auf die eine Metalla-Nazarov-Reaktion und eine elektrophile Cyclopropanierung folgen sollten.…”

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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“…To this purpose, various silver salts with poorly coordinating counterions were added to our catalytic system (Table 1). With the Pt/(R,S)-JOSIPHOS system (entries [10][11][12], the silver additives had a moderately positive influence on yields and ee and the use of -BF 4 and -SbF 6 salts led consistently to a fair increase of both values. For instance, the hydroxycyclization of enyne 1a gave the corresponding alcohol 2a in 62 % isolated yield in 2.5 days in up to 41 % ee (entry 12).…”

confidence: 99%

“…We then turned our attention to platinum chemistry for the asymmetric version and investigated the functionalization of enyne 1a with platinum in the presence of several chiral phosphane ligands (Table 1) [10]. Preliminary tests were performed in dioxane/water 6:1 using 10 mol % Pt catalyst and 15 mol % of bidentate or 30 mol % of mono-dentate phosphine.…”

Section: Asymmetric Pt-catalyzed Hydroxy-and Methoxycyclization Reactmentioning

confidence: 99%

“…Thus, from the substrates 4d and 4b, the relevant methyl ethers were obtained in 78 and 50 % ee, respectively (entries 6 and 3). The absolute configurations of the alcohols obtained from hydroxycyclizations have been determined by empirical methods from the 1 H NMR spectra of the O-methylmandelate esters derived from 5d [22,10]. This asymmetric reaction is still highly challenging as no general metal/chiral ligand association is available.…”

confidence: 99%

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Alkoxy- and hydroxycyclization of enynes catalyzed by Pd(II) and Pt(II) catalysts

Michelet

Charruault

Gladiali

et al. 2006

Pure and Applied Chemistry

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The development of a novel reaction ideal in terms of atom economy was achieved. The scope of the reaction was evaluated in the presence of Pd and Pt catalysts. The first enantioselective Pt-promoted enyne carboalkoxycyclization was developed in up to 85 % stereoselectivity. This ideal atom-economical reaction afforded the corresponding functionalized five-membered carbo-and heterocycles in good to excellent yields. The use of silver salts combined with (R)-Ph-BINEPINE, a monophosphane atropisomeric ligand, was found to be the best-suited combination for moderate to high enantioselectivities on carbonated and nitrogenated substrates.

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Functionalized carbo- and heterocycles via Pt-catalyzed asymmetric alkoxycyclization of 1,6-enynes

Abstract: This paper describes the asymmetric version of highly atom-economical alkoxycyclization of 1,6-enynes, using a combination of silver salts with the Pt(II)/(R)-Ph-BINEPINE system.

Cited by 111 publications

References 28 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

Alkoxy- and hydroxycyclization of enynes catalyzed by Pd(II) and Pt(II) catalysts

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