PtCl<sub>2</sub>-Catalyzed Conversion of 1,6- and 1,7-Enynes to 1-Vinylcycloalkenes. Anomalous Bond Connection in Skeletal Reorganization of Enynes

Chatani, Naoto; Furukawa, N.; Sakurai, and Hitoshi; Murai, Shinji

doi:10.1021/om950832j

Cited by 230 publications

(112 citation statements)

References 17 publications

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“…[5] Two years later, the same group reported that PtCl 2 efficiently catalyzed cycloisomerizations of 1,6-and 1,7-enynes to 1-vinylcycloalkenes (Scheme 3). [6] In a typical experiment described in this report, treatment of enyne 5 with 4 mol % of PtCl 2 in toluene at 80 8C under a nitrogen atmosphere afforded the cyclorearranged product 6 in 86 % yield. A representative scope of this process is depicted in Scheme 3.…”

Section: Introductionmentioning

confidence: 80%

“…[6] This anomalous result of the skeletal reorganization corresponded to the formal insertion of the methylene group of the alkene between the two carbons of the alkynes. While no mechanistic rational was provided by Murai and co-workers at the time, the outcome of these experiments has been rationalized (see Scheme 14).…”

Section: Scheme 2 a C H T U N G T R E N N U N G (Pphmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 80%

Section: Scheme 2 a C H T U N G T R E N N U N G (Pphmentioning

confidence: 99%

Gold and Platinum Catalysis of Enyne Cycloisomerization

2006

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“…[117] A rather wide variety of enynes was found to undergo cyclorearrangement in toluene at 80 8C over 1-20 h [Eq. (98)- (100)].…”

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

927

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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“…[287] Dem folgten rasch vergleichbare Beobachtungen von Murai, Chatani und Mitarbeitern unter Verwendung von Rutheniumkomplexen oder Platinsalzen als Katalysatoren. [288,289] Dass sich derartige Reaktionen mechanistisch sowohl von der klassischen Metathese als auch von Alder-EnReaktionen grundlegend unterscheiden, wurde an der Bildung eine Reihe unerwarteter Produktstrukturen rasch deutlich: [289] so lieferte etwa die Umsetzung des Enins 303 die beiden regioisomeren Ester 304 und 305. Im Zug einer Synthese des Pyrrolalkaloids Streptorubin (siehe auch Abschnitt 5.1) wurde erstmals ein vereinheitlichtes Erklärungsschema vorgestellt, aus dem sich die Fülle strukturell höchst unterschiedlicher Produkte zwanglos ableiten lässt (Schema 60).…”

Section: Angewandte Chemieunclassified

Katalytische carbophile Aktivierung: Platin‐ und Gold‐π‐Säuren als Katalysatoren

2007

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Platin‐ und Goldkatalysatoren gewinnen aufgrund ihrer hohen Effizienz und erstaunlichen Vielfalt für atomökonomische Umsetzungen rasch an Bedeutung. Dabei erlaubt es die Korrelation zwischen ihrem chemischen Verhalten und den vorhandenen Strukturdaten, der bekannten Koordinationschemie und den auf relativistischen Effekten beruhenden Besonderheiten ihrer metallorganischen Derivate, grundlegende Prinzipien der katalytischen carbophilen Aktivierung durch π‐Säuren zu formulieren. Platin‐ und Goldkomplexe sind keinesfalls nur ein umweltfreundlicher Ersatz für stöchiometrische π‐Säuren, sondern sie erweitern das klassische Reaktivitätsspektrum signifikant. Die in der Literatur geläufigen, aber scheinbar widersprüchlichen Erklärungen ihres Verhaltens auf Basis von Metallcarbenen oder metallstabilisierten, “nichtklassischen” Carbokationen als reaktiven Zwischenstufen liefern bei genauer Betrachtung eine vereinheitlichte Grundlage für das Verständnis dieses faszinierenden Gebiets. Hier gilt das Hauptaugenmerk der Verbesserung bekannter sowie der Entwicklung neuer Kupplungs‐, Cycloisomerisierungs‐ und Gerüstumlagerungsreaktionen. Auch der Einsatz Platin‐ und goldkatalysierter Transformationen in Naturstoffsynthesen wird diskutiert.

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PtCl₂-Catalyzed Conversion of 1,6- and 1,7-Enynes to 1-Vinylcycloalkenes. Anomalous Bond Connection in Skeletal Reorganization of Enynes

Cited by 230 publications

References 17 publications

Gold and Platinum Catalysis of Enyne Cycloisomerization

Gold and Platinum Catalysis of Enyne Cycloisomerization

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

Katalytische carbophile Aktivierung: Platin‐ und Gold‐π‐Säuren als Katalysatoren

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PtCl2-Catalyzed Conversion of 1,6- and 1,7-Enynes to 1-Vinylcycloalkenes. Anomalous Bond Connection in Skeletal Reorganization of Enynes

Cited by 230 publications

References 17 publications

Gold and Platinum Catalysis of Enyne Cycloisomerization

Gold and Platinum Catalysis of Enyne Cycloisomerization

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

Katalytische carbophile Aktivierung: Platin‐ und Gold‐π‐Säuren als Katalysatoren

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PtCl₂-Catalyzed Conversion of 1,6- and 1,7-Enynes to 1-Vinylcycloalkenes. Anomalous Bond Connection in Skeletal Reorganization of Enynes