Novel 1,3-Diene Synthesis from Alkyne and Ethylene by Ruthenium-Catalyzed Enyne Metathesis

Kinoshita, Atsushi; Sakakibara, Norikazu; Mori, Miwako

doi:10.1021/ja973134u

Cited by 176 publications

(66 citation statements)

References 43 publications

(5 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[23] Internal alkynes were used predominantly in this study. This method also utilized the first generation Grubbs' carbene as initiator for this cross metathesis.…”

Section: Enyne Metathesismentioning

confidence: 99%

Ruthenium vinyl carbene intermediates in enyne metathesis

Diver

2007

Coordination Chemistry Reviews

View full text Add to dashboard Cite

This review provides an overview of ruthenium vinyl carbene reactivity as it relates to enyne metathesis. Methods for the synthesis of metathesis-active and metathesis-inactive complexes are also summarized. Some of the early hypotheses about vinyl carbene intermediates in enyne metatheses were tested in the arena of synthetic chemistry and subsequently led to mechanistic studies. In these two areas, studies from the author's labs are described. There are still many unresolved questions in enyne metathesis that trace back to vinyl carbene reactivity. Hopefully this review will stimulate further investigation into vinyl carbene reactivity which should further refine our understanding of catalytic enyne metathesis.

show abstract

“…[23] Internal alkynes were used predominantly in this study. This method also utilized the first generation Grubbs' carbene as initiator for this cross metathesis.…”

Section: Enyne Metathesismentioning

confidence: 99%

Ruthenium vinyl carbene intermediates in enyne metathesis

Diver

2007

Coordination Chemistry Reviews

View full text Add to dashboard Cite

show abstract

“…Furthermore, under an ethylene atmosphere (32,33), intermolecular ene-yne metatheses have been shown to proceed by ethylene-yne cross metathesis followed by a terminal diene-olefin cross metathesis (28). We believe that our system behaves similarly: ethylene-yne cross metathesis occurs first, affording a terminal 1,3-diene, followed by terminal diene-olefin metathesis macrocyclization.…”

Section: Resultsmentioning

confidence: 71%

Synthesis of (-)-longithorone A: Using organic synthesis to probe a proposed biosynthesis

Morales

Layton

Shair

2004

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

We present a full report of our enantioselective synthesis of (؊)-longithorone A (1). The synthesis was designed to test the feasibility of the biosynthetic proposal for 1 put forward by Schmitz involving intermolecular and transannular Diels-Alder reactions of two [12]-paracyclophane quinones. We have found that if the biosynthesis does involve these two Diels-Alder reactions, the intermolecular Diels-Alder reaction likely occurs before the transannular cycloaddition. The intermolecular Diels-Alder precursors, [12]-paracyclophanes 38, 49, 59, and 60, were prepared atropselectively, providing examples of ene-yne metathesis macrocyclization. The 1,3-disubstituted dienes produced from the macrocyclizations represent a previously unreported substitution pattern for intramolecular ene-yne metathesis. Protected benzylic hydroxyl stereocenters were used as removable atropisomer control elements and were installed by using a highly enantioselective vinylzinc addition to electron-rich benzaldehydes 26 and 27.A n intriguing question in natural product biosynthesis is whether nature uses Diels-Alder reactions. The answer to this question appears to be yes, because there are many examples of spontaneous Diels-Alder reactions in biosyntheses (1) as well as recently documented examples (2-4) of enzymatically influenced Diels-Alder reactions. Longithorone A (1) is a marine natural product that attracted our attention because of its unusual structure, but even more so because of the biosynthetic proposal of Schmitz and co-workers (5, 6) that invoked two Diels-Alder reactions. Schmitz has proposed that 1 arises from the combination of [12]-paracyclophane quinones 2 and 3 by an intermolecular Diels-Alder reaction, affording ring E, and a transannular (7) Diels-Alder reaction, generating rings A, C, and D (Fig. 1).We viewed this interesting proposal as an opportunity to use organic synthesis to make protected versions of 2 and 3 and test, in the laboratory, the feasibility of the proposed Diels-Alder reactions (8). In particular, we were hopeful that our experiments might suggest whether the intermolecular Diels-Alder reaction occurs preferentially between compound 4, which has already undergone a transannular Diels-Alder, and paracyclophane 2 to generate 1 or between paracyclophanes 3 and 2 to generate 5, followed by a transannular Diels-Alder to afford 1.The isolation (5) of longithorones B (9) and C, [12]-paracyclophane quinones that closely resemble the structures of 2 and 3, provided some support for the proposed biosynthesis of longithorone A (Fig. 2).We found it intriguing that longithorones B and C exhibit atropisomerism (10-12) and are single enantiomers. From these observations, we recognized that 2 and 3 must be constructed atropselectively to test whether the absolute and relative stereochemistry of 1 is derived solely from the planar chirality of 2 and 3. Finally, the isolation of longithorone I suggested that the biosynthesis of 1 may first involve an intermolecular Diels-Alder reaction between 2 and 3 followed by a...

show abstract

“…[57] Die Synthesevorschrift ist insofern äußerst attraktiv, als dass lediglich eine Lçsung des Alkins und des Rutheniumkatalysators bei Raumtemperatur unter 1 atm Ethylen gerührt werden muss. In der Gesamttransformation fügt sich jeweils ein Kohlenstoffatom des Ethylens an beide sp-hybridisierte Alkinkohlenstoffatome an.…”

Section: Ausbeuten Erhalten (Schema 22)unclassified

Übergangsmetallkatalysierte C‐C‐Kupplungen mit Ethylen im Labormaßstab

2013

View full text Add to dashboard Cite

Ethylen ist das (volumenbezogen) in größter Menge synthetisierte organische Molekül. Es lässt sich leicht in übergangsmetallkatalysierte C‐C‐Kupplungsreaktionen einbinden, und zwar durch migratorische Insertion in Alkylmetall‐Intermediate. Wegen der D2h‐Symmetrie des Ethylens kann die Insertion nur einen einzigen Verlauf nehmen, was die Nebenproduktbildung limitiert und die Produktanalyse außerordentlich vereinfacht. Wie in diesem Kurzaufsatz beschrieben wird, wird bei vielen C‐C‐Kupplungen das Ethylenmolekül (oder mehrere) bei Umgebungsdruck und ‐temperatur eingefügt. Auch sind viele Reaktionen bekannt, bei denen ein in geeigneter Weise substituiertes Alken in das Produkt eingeführt wird.

show abstract

Novel 1,3-Diene Synthesis from Alkyne and Ethylene by Ruthenium-Catalyzed Enyne Metathesis

Cited by 176 publications

References 43 publications

Ruthenium vinyl carbene intermediates in enyne metathesis

Ruthenium vinyl carbene intermediates in enyne metathesis

Synthesis of (-)-longithorone A: Using organic synthesis to probe a proposed biosynthesis

Übergangsmetallkatalysierte C‐C‐Kupplungen mit Ethylen im Labormaßstab

Contact Info

Product

Resources

About