Palladium-Catalyzed [3+2] Intramolecular Cycloaddition of Alk-5-ynylidenecyclopropanes:  A Rapid, Practical Approach to Bicyclo[3.3.0]octenes

Delgado, Alejandro; Rodríguez, Jéssica; Castedo, Luís; Mascareñas, José L.

doi:10.1021/ja0356333

Cited by 103 publications

(28 citation statements)

References 12 publications

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“…A 1,2-hydride shift and elimination complete the catalytic cycle to form a diene of type 52, which corresponds to path D. The hypothesis supporting the existence of intermediate 50 has been backed up through the trapping of analogues by conjugated dienes. [30] Finally, Mascareaeas and co-workers [31] have described the synthesis of a bicycle based on the specific reactivity of alkynylidenecyclopropanes. The addition of enyne 53 to a combination of a Pd 0 source and a bulky phosphite such as 55 led to the formation of 1,4-diene 54 [Eq.…”

Section: Reviewsmentioning

confidence: 99%

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

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

940

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: Reviewsmentioning

confidence: 99%

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

Michelet¹,

Toullec²,

Genêt³

2008

Angew Chem Int Ed

940

248

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“…Da bei palladiumkatalysierten Umsetzungen die Diene aus diesen beiden Reaktionswegen häufig als Gemisch erhalten werden, sollten die Reaktionen am besten als "Gerüstumlagerungen" bezeichnet werden. [26] 1988 beschrieben Trost und Tanoury [27] die [30] Schließlich beschrieben Mascareaeas et al [31] eine Bicyclensynthese, die auf der spezifischen Reaktivität von Alkinylidencyclopropanen beruht. Die Zugabe des Enins 53 zu einer Pd 0 -Quelle in Kombination mit einem sperrigen Phosphit wie 55 ergab das 1,4-Dien 54 [Gl.…”

Section: Enin-umlagerungenunclassified

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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“…[89] Despite the large amount of literature regarding palladium(0)-catalyzed nucleophilic substitutions of allylic acetates or analogues, the use of amines as nucleophiles has been only of comparatively limited interest. In particular, the use of amino acids as nucleophiles has been employed for the first time by Brandi et al In this study, the tosylate 129 underwent Pd(0)-catalyzed nucleophilic substitution of a-amino and ahydroxy acid derivatives 131a-h to afford exclusively the corresponding alkylidenecyclopropanes 132a-h. [90] As shown in Scheme 44, high yields of 132a-h were obtained by using a series of eight a-amino esters 131a-g and the methyl glycolate 131h.…”

Section: Through Transition Metal Allyl Complexesmentioning

confidence: 99%

Synthesis of Methylene‐ and Alkylidenecyclopropane Derivatives

Audran

Pellissier

2010

Adv Synth Catal

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Since the methylenecyclopropane moiety is found in many biologically active natural substances, the synthesis of methylene-and alkylidenecyclopropanes remains a considerable challenge. In addition, an attractive feature is their surprising stability, accompanied by a high level of strain, conferring on them an otherwise unattainable chemical reactivity. The growing interest in the chemistry of these compounds has in its turn stimulated the development of alternative approaches to their skeleton, aimed at selectively introducing structural and chemical diversification. The three principal methods to synthesize these important compounds are based on the formation of the cyclopropane ring, the use of preformed cyclopropanes, and the use of preformed methyleneand alkylidenecyclopropanes.

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Palladium-Catalyzed [3+2] Intramolecular Cycloaddition of Alk-5-ynylidenecyclopropanes: A Rapid, Practical Approach to Bicyclo[3.3.0]octenes

Abstract: Readily accessible hex-5-ynylidenecyclopropane derivatives cycloisomerize to bicyclic five-membered carbocycles upon heating with catalytic amounts of a palladium complex.

Cited by 103 publications

References 12 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

Synthesis of Methylene‐ and Alkylidenecyclopropane Derivatives

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