Syntheses of Anolignans A and B Using Ruthenium-Catalyzed Cross-Enyne Metathesis

Mori, Miwako; Tonogaki, Keisuke; Nishiguchi, Nao

doi:10.1021/jo0107913

Cited by 84 publications

(33 citation statements)

References 15 publications

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“…[104] In the presence of 6 (3-10 %) as a catalyst, both terminal and internal alkenes were found to be active, furnishing butadiene adducts in moderate to good yields. [105] The presence of a heteroatom in the propargylic position was critical for high product yield. Substrates with ester or amide heterofunctions gave goods results, whereas ether or amine heteroatoms completely prevented any conversion, most likely via metathesis-inactive chelated intermediates.…”

Section: Intermolecular Enyne Metathesismentioning

confidence: 99%

Recent Developments in Olefin Cross‐Metathesis

2003

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Among the many types of transition-metal-catalyzed C-C bond-forming reactions, olefin metathesis has come to the fore in recent years owing to the wide range of transformations that are possible with commercially available and easily handled catalysts. Consequently, olefin metathesis is now widely considered as one of the most powerful synthetic tools in organic chemistry. Until recently the intermolecular variant of this reaction, cross-metathesis, had been neglected despite its potential. With the evolution of new catalysts, the selectivity, efficiency, and functional-group compatibility of this reaction have improved to a level that was unimaginable just a few years ago. These advances, together with a better understanding of the mechanism and catalyst-substrate interactions, have brought us to a stage where more and more researchers are employing cross-metathesis reactions in multistep procedures and in the synthesis of natural products. The recent inclusion of alkynes and hindered bicyclic olefins as viable substrates for bimolecular metathesis coupling, the discovery of enantioselective cross-metathesis and cross-metathesis in water, and the successful marriage of metathesis and solid-phase organic synthesis has further widened the scope of this versatile reaction.

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Section: Intermolecular Enyne Metathesismentioning

confidence: 99%

Recent Developments in Olefin Cross‐Metathesis

2003

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“…It was interesting that the two methylidene parts of the anolignane skeleton could be introduced at the last stage of the total synthesis using cross-metathesis (Scheme 23). [47] A short and efficient synthesis of highly substituted tetrahydropyridines 85 was achieved from a monosubstituted alkyne, a terminal alkene, and an imine by a combination of enyne cross-metathesis and aza-DielsAlder reaction under high pressure. Cross-metathesis of a terminal alkyne and an alkene afforded diene Scheme 21.…”

Section: Synthesis Of Natural Products and Related Compounds Using DImentioning

confidence: 99%

Synthesis of Natural Products and Related Compounds using Enyne Metathesis

Mori

2007

Adv Synth Catal

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148

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Since the molybdenum and ruthenium carbene complexes 1a and 1b were discovered by Schrock and Grubbs in 1990 and 1992, synthetic organic chemistry has progressed with the use of these complexes as the catalyst for olefin metathesis. It was found that the ruthenium carbene complex was also effective for enyne metathesis, which occurs between an alkene and an alkyne. Intramolecular enyne metathesis gives various cyclic compounds having a 1,3-diene moiety and cross-metathesis of an alkene with an alkyne is a useful method for the synthesis of a compound having a diene moiety. Furthermore, dienyne metathesis, ROM of cycloalkenynes or tandem reactions of enyne metathesis have been developed. Using these various enyne metatheses, complicated natural products have been synthesized via novel routes. The syntheses of natural products and related compounds using enyne metathesis are described.

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“…[105] Entscheidend für hohe Produktausbeuten war die Anwesenheit eines Heteroatoms in propargylischer Stellung. Substrate mit Ester-oder Amid-Heterofunktionen führten zu guten Ergebnissen, wäh-rend Umsetzungen mit Ethern oder Aminen vermutlich wegen der Bildung inaktiver Chelatzwischenstufen nicht gelangen.…”

Section: Intermolekulare En-in-metathesenunclassified

Jüngste Entwicklungen bei der gekreuzten Olefinmetathese

2003

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Unter den vielen übergangsmetallvermittelten C‐C‐verknüpfenden Reaktionen ist die Olefinmetathese in den letzten Jahren durch die große Bandbreite an möglichen Umsetzungen mit käuflichen und leicht handhabbaren Katalysatoren hervorgetreten und gilt heutzutage als eine der mächtigsten Synthesemethoden in der Organischen Chemie. Die intermolekulare Variante dieser Reaktion, die Kreuzmetathese, führte trotz ihres hohen synthetischen Nutzens bis vor kurzem eher ein Schattendasein. Durch die Entwicklung neuer, besserer Katalysatoren konnte die Selektivität, die Toleranz gegen funktionelle Gruppen und die Effizienz der Katalyse jedoch auf ein Niveau gesteigert werden, das noch bis vor wenigen Jahren als unvorstellbar galt. Dank dieser Fortschritte und dem verbesserten Verständnis des Reaktionsmechanismus und der Katalysator‐Substrat‐Wechselwirkungen werden Kreuzmetathesen heute in zunehmendem Maße in mehrstufigen Reaktionssequenzen und Naturstoffsynthesen verwendet. Die kürzlich vorgestellte Einbeziehung von Alkinen und sterisch gehinderten bicyclischen Olefinen als Substrate für bimolekulare Kupplungen, die Entwicklung von enantioselektiven und in Wasser ausführbaren Kreuzmetathesen und die erfolgreiche Kombination der Olefinmetathese und der Festphasensynthese in der Organischen Chemie haben die Anwendungsbreite der Kreuzmetathese noch zusätzlich vergrößert.

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Syntheses of Anolignans A and B Using Ruthenium-Catalyzed Cross-Enyne Metathesis

Abstract: Anolignans A and B were synthesized using ruthenium-catalyzed cross-enyne metathesis as the key steps. The 1,3-diene moieties of these natural products were constructed by the introduction of the methylene parts of ethylene into alkyne using Grubbs' catalyst.

Cited by 84 publications

References 15 publications

Recent Developments in Olefin Cross‐Metathesis

Recent Developments in Olefin Cross‐Metathesis

Synthesis of Natural Products and Related Compounds using Enyne Metathesis

Jüngste Entwicklungen bei der gekreuzten Olefinmetathese

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