Solvent-free isomerization of allylic alcohols catalyzed by a rhodium catalyst-organic framework

Corkum, Elizabeth G.; Kalapugama, Suneth; Hass, Michael J.; Bergens, Steven H.

doi:10.1039/c2ra20197f

Cited by 17 publications

(7 citation statements)

References 66 publications

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“…However, the requirement of a hydrogen atmosphere resulted in low selectivities toward the desired carbonyl compounds, due to the occurrence of hydrogenation and hydrogenolysis reactions in competition [14]. A much more general, selective, and efficient system (TOF up to 6400 h −1 ), consisting of a rhodium complex immobilized onto a ligand-polymer support, has been recently reported by Bergens and co-workers [15]. Unfortunately, despite the remarkable efficiency showed by this polymeric material, its recycling was not demonstrated.…”

Section: Introductionmentioning

confidence: 99%

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

Menéndez-Rodríguez

Crochet

Cadierno

2013

Journal of Molecular Catalysis A: Chemical

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Section: Introductionmentioning

confidence: 99%

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

Menéndez-Rodríguez

Crochet

Cadierno

2013

Journal of Molecular Catalysis A: Chemical

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“…Rhodium complexes have been applied in numerous industrially significant reactions of hydrogenation [9], dehydrogenation of primary alcohols [10], hydroamination [11] and hydroformylation [12,13]. Bergens and co-workers reported an immobilized rhodium catalyst-organic framework for solvent-free isomerization of allylic alcohols [14]. A water soluble complex which forms during the reaction of [Rh(cod)(CH 3 CN) 2 ]BF 4 (cod = η 4 -cyclo-1,5-octadiene) and pta (1,3,5-triaza-7-phosphaadamantane) catalyzes the isomerization of codeine and morphine into hydrocodone and hydromorphone, which is an important transformation from a pharmaceutical point of view [15].…”

Section: Introductionmentioning

confidence: 99%

Redox Isomerization of Allylic Alcohols Catalyzed by New Water-Soluble Rh(I)-N-Heterocyclic Carbene Complexes

Czégéni¹,

Fekete

Tóbiás

et al. 2020

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New water-soluble, N-heterocyclic carbene (NHC) or mixed NHC/tertiary phosphine complexes [RhCl(cod)(sSIMes)], Na2[Rh(bmim)(cod)(mtppts)], and [Rh(bmim)(cod)(pta)]BF4 were synthetized and applied for the first time as catalysts in redox isomerization of allylic alcohols in aqueous media. [RhCl(cod)(sSIMes)] (with added sulfonated triphenylphosphine) and [Rh(bmim)(cod)(pta)]BF4 catalyzed selectively the transformation of allylic alcohols to the corresponding ketones. The highest catalytic activity, TOF = 152 h−1 (TOF = (mol reacted substrate) × (mol catalyst × time)−1) was observed in redox isomerization of hept-1-en-3-ol ([S]/[cat] = 100). The catalysts were reused in the aqueous phase at least three times, with only modest loss of the catalytic activity and selectivity.

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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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Solvent-free isomerization of allylic alcohols catalyzed by a rhodium catalyst-organic framework

Cited by 17 publications

References 66 publications

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

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

Redox Isomerization of Allylic Alcohols Catalyzed by New Water-Soluble Rh(I)-N-Heterocyclic Carbene Complexes

Theoretical investigation for isomerization of allylic alcohols over Au6 cluster

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