Tandem olefin metathesis/hydrogenation at ambient temperature: activation of ruthenium carbene complexes by addition of hydrides

Schmidt, Bernd; Pohler, Michael

doi:10.1039/b303441k

Cited by 72 publications

(37 citation statements)

References 26 publications

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“…8, the choice of solvent has a major influence on the product distribution under otherwise identical conditions at 280°C. While the Claisen rearrangement 1 → 2 was complete in all solvents with no starting allyl phenyl ether remaining, aromatic solvents such as toluene apparently facilitated double bond migration in the side chain leading to substantial amounts of 2-(prop-1-enyl)phenols (3) and (4) [82]. In EtOH, the reaction was remarkably clean, even at 280°C, while in DME, Fig.…”

Section: Claisen Rearrangement Of Allyl Phenyl Ethermentioning

confidence: 93%

Accessing Novel Process Windows in a High‐Temperature/Pressure Capillary Flow Reactor

2009

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High-temperature/pressure organic synthesis can be performed under continuous flow conditions in a stainless steel microtubular flow reactor capable of achieving temperatures of 350°C and 200 bar (X-Cube Flash™). Using these extreme experimental environments, the Claisen rearrangement of allyl phenyl ether together with the ensuing rearrangement chemistry of the resulting 2-allylphenol product was investigated. Reaction optimization was performed by changing the temperatures, pressures and flow rates "on-the-fly". In addition, the high-temperature/pressure flow system allowed the study of these transformations in low boiling point solvents in or near their supercritical state. In general, the chemistry optimized under high-temperature microwave batch conditions could be successfully translated to a scalable flow regime.

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Section: Claisen Rearrangement Of Allyl Phenyl Ethermentioning

confidence: 93%

Accessing Novel Process Windows in a High‐Temperature/Pressure Capillary Flow Reactor

2009

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“…This point is illustrated by the synthesis of cyclopentanes (e.g., 137) from diallylcarbinols (e.g., 136) (Scheme 37). [109] Scheme 37. Activation of Ru metathesis catalysts for hydrogenation reactions at ambient temperature by addition of hydrides …”

Section: Application Of Sequential Rcm/hydrogenationmentioning

confidence: 99%

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

2004

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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.

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“…In an alternative approach, activation of the metathesis catalyst for hydrogenation has been achieved by using inorganic hydrides as additives in a RCM/hydrogenation sequence [37]. For instance, sodium hydride effectively activates ruthenium carbene complexes to catalyze hydrogenation reactions subsequent to ring closing olefin metathesis.…”

Section: Tandem and Sequential Metathesis/hydrogenationmentioning

confidence: 99%

A resourceful new strategy in organic synthesis: Tandem and stepwise metathesis/non-metathesis catalytic processes

Drăguţan

2006

Journal of Organometallic Chemistry

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Tandem olefin metathesis/hydrogenation at ambient temperature: activation of ruthenium carbene complexes by addition of hydrides

Cited by 72 publications

References 26 publications

Accessing Novel Process Windows in a High‐Temperature/Pressure Capillary Flow Reactor

Accessing Novel Process Windows in a High‐Temperature/Pressure Capillary Flow Reactor

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

A resourceful new strategy in organic synthesis: Tandem and stepwise metathesis/non-metathesis catalytic processes

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