Catalytically Reactive Ruthenium Intermediates in the Homogeneous Oxidation of Alcohols to Esters

Blum, Yigal D.; Shvo, Youval

doi:10.1002/ijch.198400024

Cited by 70 publications

(26 citation statements)

References 17 publications

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“…The complex [(C 4 Ph 4 CO)(CO) 2 Ru] 2 (7) reacts with alcohols to give the hydrogen-loaded dimer [(C 4 Ph 4 CO-HOCC 4 Ph 4 )(µ-H)(CO) 4 Ru 2 ] (8) and the monomeric ruthenium hydride complex [(C 4 Ph 4 COH)(CO) 2 RuH] (9) (Scheme 3), and it has also been shown to be an active catalyst for the dehydrogenation of primary alcohols to esters, [17] the disproportionation of aldehydes to esters, [16] and the oxidation of secondary alcohols to ketones. [ reactive intermediates (9 and 10) or catalyst resting states (7 and 8).…”

Section: Rationale For the Selection Of Catalystmentioning

confidence: 99%

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

Bierenstiel

Schlaf

2004

Eur J Org Chem

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δ‐D‐Gluconolactone, δ‐D‐mannonolactone, and — for the first time — the thermodynamically unstable δ‐D‐galactonolactone have been prepared and isolated from DMF solution by oxidizing the corresponding sugars with Shvo’s catalyst [(C4Ph4CO)(CO)2Ru]2 and a hydrogen acceptor. The preferred conformation of δ‐D‐galactonolactone in [D6]DMSO solution has been determined by 1H NMR spectroscopy experiments and DFT calculations to be 4H3 and is compared to those of the previously established conformations of δ‐D‐gluconolactone (4H3) and δ‐D‐mannonolactone (B2,5). The conformations of the lactones suggest an explanation for their relative rates of isomerization to their respective γ‐D‐lactones by an intramolecular mechanism. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Rationale For the Selection Of Catalystmentioning

confidence: 99%

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

Bierenstiel

Schlaf

2004

Eur J Org Chem

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“…It was first synthesized in 1984 by Shvo et al [1,2]. Since then it has been widely applied in various hydrogen transfer reactions, including hydrogenation of carbonyl compounds [2,3], transfer hydrogenation of ketones and imines [4,5], disproportion of aldehydes to esters [6], and Oppenauer-type oxidations of alcohols [7][8][9] and amines [10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Shvo’s Catalyst in Hydrogen Transfer Reactions

Warner

Casey

Bäckvall

2011

Bifunctional Molecular Catalysis

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This chapter reviews the use of Shvo's catalyst in various hydrogen transfer reactions and also discusses the mechanism of the hydrogen transfer. The Shvo catalyst is very mild to use since no activation by base is required in the transfer hydrogenation of ketones or imines or in the transfer dehydrogenation of alcohols and amines. The Shvo catalyst has also been used as an efficient racemization catalyst for alcohols and amines. Many applications of the racemization reaction are found in the combination with enzymatic resolution leading to a dynamic kinetic resolution (DKR). In these dynamic resolutions, the yield based on the starting material can theoretically reach 100%. The mechanism of the hydrogen transfer from the Shvo catalyst to ketones (aldehydes) and imines as well as the dehydrogenation of alcohols and amines has been studied in detail over the past decade. It has been found that for ketones (aldehydes) and alcohols, there is a concerted transfer of the two hydrogens involved, whereas for typical amines and imines, there is a stepwise transfer of the two hydrogens. One important question is whether the substrate is coordinated to the metal or not in the hydrogen transfer step(s). The pathway involving coordination to activate the substrate is called the inner-sphere mechanism, whereas transfer of hydrogen without coordination is called the outer-sphere mechanism. These mechanistic proposals together with experimental and theoretical studies are discussed.

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“…Complexes 1-3 [12][13][14], 4a [15,16], 4b [17], 6 [18], 7 [19], 8a-c [20] were prepared according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Ruthenacycles and Iridacycles as Catalysts for Asymmetric Transfer Hydrogenation and Racemisation

et al. 2010

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Ruthenacycles, which are easily prepared in a single step by reaction between enantiopure aromatic amines and [Ru(arene)Cl 2 ] 2 in the presence of NaOH and KPF 6 , are very good asymmetric transfer hydrogenation catalysts. A range of aromatic ketones were reduced using isopropanol in good yields with ee's up to 98%. Iridacycles, which are prepared in similar fashion from [IrCp*Cl 2 ] 2 are excellent catalysts for the racemisation of secondary alcohols and chlorohydrins at room temperature. This allowed the development of a new dynamic kinetic resolution of chlorohydrins to the enantiopure epoxides in up to 90% yield and 98% enantiomeric excess (ee) using a mutant of the enzyme Haloalcohol dehalogenase C and an iridacycle as racemisation catalyst.

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Catalytically Reactive Ruthenium Intermediates in the Homogeneous Oxidation of Alcohols to Esters

Cited by 70 publications

References 17 publications

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

δ‐Galactonolactone: Synthesis, Isolation, and Comparative Structure and Stability Analysis of an Elusive Sugar Derivative

Shvo’s Catalyst in Hydrogen Transfer Reactions

Ruthenacycles and Iridacycles as Catalysts for Asymmetric Transfer Hydrogenation and Racemisation

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