Catalytic isomerization of allylic alcohols promoted by complexes [RuCl2(η6-arene)(PTA-Me)] under homogeneous conditions and supported on Montmorillonite K-10

Menéndez-Rodríguez, Lucía; Crochet, Pascale; Cadierno, Victorio

doi:10.1016/j.molcata.2012.10.025

Cited by 25 publications

(19 citation statements)

References 81 publications

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“…Since a poorly soluble base is used for activation, [16] an induction period is observed that corresponds to formation of the active species. [12] To minimize this effect and obtain more easily comparable results, the catalyst was preheated with Cs 2 CO 3 in THF for 5 min at 60 8C. Both 2-ML and 2-G 1 show high catalytic activity in the conversion of 1-octen-3-ol to 3octanone, but the dendritic catalyst 2-G 1 shows higher activity than 2-ML (60 min, TOF 400) and leads to full conversion after 40 min (TOF 600).…”

Section: Methodsmentioning

confidence: 99%

“…[11] Besides rhodium(I), ruthenium(II) is predominantly used for this transformation. [12] This reaction has already been applied in numerous multistep syntheses, [13] as well as with metallodendritic catalysts. [14] Complexes such as [(h 6 -arene)RuCl 2 (L)], in which L is a monodentate phosphane ligand (PPh 3 or analogues), show particularly high activity.…”

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confidence: 99%

“…[14] Complexes such as [(h 6 -arene)RuCl 2 (L)], in which L is a monodentate phosphane ligand (PPh 3 or analogues), show particularly high activity. [12,15] Scheme 1. Redox reaction of the dendritic catalyst 2-G 1 (green = active catalyst; red = poorly active ligand).…”

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confidence: 99%

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Redox Control of a Dendritic Ferrocenyl‐Based Homogeneous Catalyst

et al. 2014

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The application of a dendrimer in a redox-switchable catalytic process is reported. A monomeric and the corresponding dendritic ferrocenylphosphane ligand were used to develop well-defined controllable catalysts with distinct redox states. The corresponding ruthenium(II) complexes catalyze the isomerization of the allylic alcohol 1-octen-3-ol. By adding a chemical oxidant or reductant, it was possible to reversibly switch the catalytic activity of the complexes. On oxidation, the ferrocenium moiety withdraws electron density from the phosphane, thereby lowering its basicity. The resulting electron-poor ruthenium center shows much lower activity for the redox isomerization and the reaction rate is markedly reduced.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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Redox Control of a Dendritic Ferrocenyl‐Based Homogeneous Catalyst

et al. 2014

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“…While this conventional reaction contains a two-step sequential oxidation and reduction, isomerization of allylic alcohols enables single-step transformation. Therefore, various catalysts which contain Ru and Rh have been developed for this purpose [1][2][3][4][5][6][7][8][9][10][11]. Isomerization of allyl alcohol could also be used for a catalytic irreversible hydrolysis of allyl esters [3].…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation for isomerization of allylic alcohols over Au6 cluster

et al. 2015

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Transformation of allylic alcohols to corresponding saturated carbonyl compounds is one of the important reactions for industrial processes. Lately, Au-supported catalysts exhibit the catalytic activity for the isomerization of allylic alcohols to saturated aldehydes. However, the detail catalytic mechanism of this reaction was not elucidated in detail. Thus, theoretical calculations were carried out for the isomerization of 2-hexen-1-ol over isolated Au 6 cluster in order to elucidate the reaction over Au catalysts. From these calculation results, it was found that the rate determining step of the reaction process was the hydrogen elimination from OH group of allylic alcohol, and the substrate was converted to 1-hexen-1-ol on Au 6 cluster. Finally, it was also confirmed that 1-hexen-1ol was converted to the corresponding aldehyde, and its activation barrier was much smaller than that of the deprotonation from OH group of allylic alcohol.

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“…Besonders Komplexe der Form [(h 6 -Aren)RuCl 2 (L)] mit einem einzähnigen Phosphanliganden L (PPh 3 -Derivate) zeigen hohe Aktivitäten. [12,15] Aufgrund der obligatorischen Verwendung einer schlecht lçslichen anorganischen Base [16] entsteht eine Induktionsphase für die Bildung der katalytisch aktiven Spezies. [12] Um diesen Effekt zu minimieren und vergleichbare Ergebnisse zu erhalten, wurde der Katalysator mit Cs 2 CO 3 in THF für 5 min bei 60 8C vorerhitzt.…”

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Redoxkontrolle eines dendritischen Ferrocenyl‐basierten Homogenkatalysators

et al. 2014

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Es wird über die erste Anwendung eines dendritischen Katalysators in einem redoxschaltbaren katalytischen Prozess berichtet. Dafür wurden unter Ausnutzung der Redoxeigenschaften des Ferrocens ein monomerer sowie der entsprechende dendritische Ferrocenylphosphanligand entwickelt. Die katalytische Aktivität der Ruthenium(II)-Komplexe konnte durch chemische Oxidation bzw. Reduktion der Ferroceneinheit reversibel geschaltet werden. Die oxidierte Ferroceniumeinheit entzieht dem Phosphan über das konjugierte p-System Elektronendichte und senkt somit dessen Basizität. Das dadurch entstehende elektronenarme Rutheniumatom zeigt eine deutlich abgeschwächte Aktivität, die Reaktionsgeschwindigkeit wird drastisch gesenkt.Hintergrundinformationen zu diesem Beitrag sind im WWW unter http://dx.

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Catalytic isomerization of allylic alcohols promoted by complexes [RuCl2(η6-arene)(PTA-Me)] under homogeneous conditions and supported on Montmorillonite K-10

Cited by 25 publications

References 81 publications

Redox Control of a Dendritic Ferrocenyl‐Based Homogeneous Catalyst

Redox Control of a Dendritic Ferrocenyl‐Based Homogeneous Catalyst

Theoretical investigation for isomerization of allylic alcohols over Au6 cluster

Redoxkontrolle eines dendritischen Ferrocenyl‐basierten Homogenkatalysators

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