Selective Isomerization of a Terminal Olefin Catalyzed by a Ruthenium Complex: The Synthesis of Indoles through Ring‐Closing Metathesis

Arisawa, Mitsuhiro; Terada, Yukiyoshi; Nakagawa, Masako; Nishida, Atsushi

doi:10.1002/anie.200290031

Cited by 191 publications

(65 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…In this case, however, the isomerization catalyst is generated in situ from the metathesis catalyst 4 by addition of vinyloxytrimethylsilane as an additive. [91] An example of isomerization and RCM occurring in a single step has been reported previously. Enamide 108, in the presence of ruthenium carbene complex 3, is cyclized to 110 and not to the expected seven-membered ring.…”

Section: Isomerization Followed By Metathesismentioning

confidence: 91%

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis

2004

View full text Add to dashboard Cite

Soon after the introduction of stable and defined ruthenium precatalysts for olefin metathesis it was discovered that double bond migrations may interfere with the metathesis reaction. This undesired side reaction has been attributed to the formation of ruthenium hydride species from metathesisactive ruthenium carbene species in situ. Over the past few years, several studies have indeed revealed the existence of pathways leading from ruthenium carbene to ruthenium hydride complexes. Furthermore, a number of examples have been published recently where typical precatalysts for olefin metathesis were found to promote non-metathesis trans- Olefin Metathesis and Non-Metathesis Side ReactionsThe discovery of stable and defined carbene complexes of molybdenum [1] and ruthenium [2] as efficient precatalysts for olefin metathesis has made this transformation one of the most important CϪC bond forming reactions.[3Ϫ8]Molybdenum-based complexes such as 1 are generally [a] formations efficiently in preparatively useful yields and selectivities, presumably via the in situ formation of ruthenium hydride species. These results open up a pathway to the development of novel catalyzed reaction sequences that combine ruthenium carbene-and ruthenium-hydride-mediated steps. This paper provides an overview of the field and covers organometallic aspects as well as synthetic applications.

show abstract

Section: Isomerization Followed By Metathesismentioning

confidence: 91%

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis

2004

View full text Add to dashboard Cite

show abstract

“…[37] Die ersten Enamine wurden dabei aus der N-Allylverbindung 64 über eine Isomerisierung in Gegenwart des Katalysators 7 und von Vinyloxytrimethylsilan synthetisiert. Das Sulfonamid 65 wurde anschließend mit 5 Mol-% 7 umgesetzt, und die RCM führte in einer Ausbeute von 83 % direkt zum substituierten Indolderivat 66.…”

Section: Direkte Bildung Anellierter Arene Durch Rcmunclassified

Ringschlussmetathese: ein Schlüssel zur Arensynthese

2006

View full text Add to dashboard Cite

Die Anwendung der Metathese, besonders der Ringschlussmetathese (RCM) zur Bildung von Fünf‐ und Sechsringen, ist heute in der organischen Chemie weit verbreitet; dennoch gibt es überraschend wenige Beispiele für ihre Anwendung zur Synthese aromatischer Verbindungen. Deren Bedeutung in der medizinischen Chemie und der Naturstoffsynthese, verbunden mit der Wirksamkeit von RCM‐Katalysatoren und ihrer Toleranz gegenüber funktionellen Gruppen, gibt Anlass, die Anwendung der RCM in der Arensynthese zu untersuchen. Die Synthese von heterocyclischen und carbocyclischen Arenen unter Verwendung der RCM wird in einigen Publikationen als Schlüsselschritt beschrieben. Galt das gebildete Aren in vielen frühen Beispielen noch als unerwünschtes Abbauprodukt, so wurden in letzter Zeit gezielt Methoden zur Arensynthese über RCM entwickelt.

show abstract

“…For more than ten years, we have been exploring a synthetic methodology for nitrogen-containing heterocycles using these ruthenium carbene catalysts and applying them to the synthesis of biologically active natural products. [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] Here, we describe our synthetic study of nitrogen-containing heterocycles using ring-closing metathesis (RCM), such as chiral bicyclic lactams, azacycloundecenes, axially chiral macrolactams, 1,2-dihydroquinolines and indoles, including the development of silyl-enol ether ene metathesis and selective isomerization of terminal olefin, and its application to the synthesis of the natural products, (Ϫ)-coniceine, (S)-pyrrolam A and angustureine.…”

Section: Development Of Syntheticmentioning

confidence: 99%

Development of Environmentally Benign Organometallic Catalysis for Drug Discovery and Its Application

Arisawa

2007

CHEMICAL & PHARMACEUTICAL BULLETIN

Self Cite

View full text Add to dashboard Cite

We have developed a novel organometallic catalysis and applied it to drug discovery. Two new catalysts were found, ruthenium hydride with a nitrogen-containing heterocyclic carbene (A) and an organopalladium catalyst supported on a sulfur-terminated semiconductor, gallium arsenide (001) (B). Both catalysts are environmentally benign, because A can yield indole derivatives with good atom economy, and B can catalyze the Mizoroki-Heck reaction more than 10 times with only trace amounts of leached palladium (ppb level). We also describe our synthetic study of nitrogen-containing heterocycles using ring-closing metathesis (RCM), such as chiral bicyclic lactams, azacycloundecenes, axially chiral macrolactams, 1,2-dihydroquinolines and indoles, including the development of silyl-enol ether ene metathesis, selective isomerization of terminal olefin, enamide metathesis and cycloisomerization and its application to the syntheis of 4 natural products, (؊)-coniceine, (S)-pyrrolam A, angustureine, and fistulosin.

show abstract

Selective Isomerization of a Terminal Olefin Catalyzed by a Ruthenium Complex: The Synthesis of Indoles through Ring‐Closing Metathesis

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 191 publications

References 36 publications

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis

Catalysis at the Interface of Ruthenium Carbene and Ruthenium Hydride Chemistry: Organometallic Aspects and Applications to Organic Synthesis

Ringschlussmetathese: ein Schlüssel zur Arensynthese

Development of Environmentally Benign Organometallic Catalysis for Drug Discovery and Its Application

Contact Info

Product

Resources

About