Formation of Gold Clusters on La–Ni Mixed Oxides and Its Catalytic Performance for Isomerization of Allylic Alcohols to Saturated Aldehydes

Ishida, Tamao; Aimoto, J.; Hamasaki, Azumi; Ohashi, Hironori; Honma, Tetsuo; Yokoyama, T.; Okumura, Mitsutaka; Tokunaga, Makoto

doi:10.1246/cl.140369

Cited by 9 publications

(5 citation statements)

References 36 publications

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“…In the third step, the imine acts as the hydrogen acceptor, and the hydrogen atom abstracted from the alcohol transfers to the imine to produce the secondary amine 89. Nitro groups90 and C=C double bonds91 also act as hydrogen acceptors. Isomerization of allylic alcohols has been reported using the intramolecular hydrogen‐borrowing strategy over Au/NiO and Au/La‐doped NiO (Scheme b) 91.…”

Section: Organic Reactions In Liquid Phasementioning

confidence: 99%

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Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Ishida

Koga

Okumura

et al. 2016

The Chemical Record

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When gold is deposited as nanoparticles (NPs) with mean diameters of 2-5 nm or clusters with mean diameters below 2 nm onto a variety of supports such as metal oxides, carbons, polymers, etc., the supported Au NPs exhibit unique catalytic properties, while bulk Au is almost inert as a catalyst. A lot of research works indicate that the key factors of the catalysis by supported Au NPs are the selection of the supports, the control of the Au NP size, the shape of the Au NPs, and the strong junction between Au NPs and the supports, because the perimeter zone around Au NPs acts as the active site for many reactions. In order to elucidate the origin of catalysis by supported Au NPs, the interplay between physicochemical analysis, computational studies, and rational experiments for catalysis by supported Au NPs is becoming more and more important. This article summarizes our experiences and progress in such interplay.

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Section: Organic Reactions In Liquid Phasementioning

confidence: 99%

“…Nitro groups90 and C=C double bonds91 also act as hydrogen acceptors. Isomerization of allylic alcohols has been reported using the intramolecular hydrogen‐borrowing strategy over Au/NiO and Au/La‐doped NiO (Scheme b) 91. Doping of La into NiO markedly improved the catalytic activity of Au.…”

Section: Organic Reactions In Liquid Phasementioning

confidence: 99%

Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Ishida

Koga

Okumura

et al. 2016

The Chemical Record

Self Cite

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Section: Introductionmentioning

confidence: 99%

“…A general overview of transition metal complexes used was recently reported (Scalambra et al, 2019 ) and these include Ru (Lorenzo-Luis et al, 2012 ), Pd (Voronova et al, 2013 ), Rh (Czégéni et al, 2020 ), and Ir (Titova et al, 2017 ). Regarding the reports in the literature on the use of heterogeneous catalysts, they are less numerous, for example, gold clusters on La–Ni mixed oxides (Ishida et al, 2014 ), supported cationic rhodium (I) complex (Sahoo et al, 2012 ), palladium nanoparticles (Maung et al, 2017 ) amorphous copper-zirconium alloy (Martinek et al, 1996 ), PdAg nanoparticles (Moreno et al, 2012 ), and Ru(OH) x /Al 2 O 3 (Kim et al, 2008 ). Some reports show that the selectivity of reaction can be influenced by different factors, namely, solvent (Yamaguchi et al, 2005 ; Hitrik and Sasson, 2018 ).…”

Section: Introductionmentioning

confidence: 99%

Ru0·Run+/Al2O3 as a Versatile Catalyst in the Isomerization of Allyl Alcohol

et al. 2021

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This study focuses on examining the isomerization of allyl alcohol using ruthenium (Ru) supported on alumina as a heterogeneous catalyst. The synthesized Ru/Al solids were characterized by various characterization techniques. The content of Ru was estimated by the energy dispersive x-ray technique. The x-ray diffraction (XRD) confirmed the presence of phases in the support and active species in the catalysts. The surface area of the support after Ru impregnation and the pore volume were determined by nitrogen physisorption. The analysis of programmed temperature (TPR and TPO) shows different redox sites which is confirmed by XPS. The catalytic results suggest a dependence on the amount of available metallic Ru, as well as the importance of the continuous regeneration of the metal using H2 to achieve a good conversion of the allyl alcohol. For comparison purposes, the commercial Ru on alumina 5% (CAS 908142) was used. The results show up to 68% alcohol conversion and 27% yield of the isomerization product using Ru(1,5.4h)/Al catalyst in comparison with 86% conversion and 39% yield of the isomerization product using CAS 908142. In contrast, our catalysts always presented higher TOF values (149–160) in comparison with CAS 908142 (101).

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“…One-pot reactions with hydrogen-borrowing strategy over Au catalysts, in which hydrogen atoms produced by the initial dehydrogenation of alcohol are used for the next step reduction, have also appeared [31][32][33][34]. Lately, Tokunaga have attempted to apply this strategy for the Au-catalyzed isomerization of trans-2-octen-1-ol to octanal [35]. However, the catalytic activity measurements do not reveal the role of Au cluster in Ausupported catalysts in detail.…”

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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Formation of Gold Clusters on La–Ni Mixed Oxides and Its Catalytic Performance for Isomerization of Allylic Alcohols to Saturated Aldehydes

Cited by 9 publications

References 36 publications

Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Advances in Gold Catalysis and Understanding the Catalytic Mechanism

Ru0·Run+/Al2O3 as a Versatile Catalyst in the Isomerization of Allyl Alcohol

Theoretical investigation for isomerization of allylic alcohols over Au6 cluster

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