Heterogeneous catalytic hydrogenation of allenes over supported palladium: selectivity, stereoselectivity, and regioselectivity

Crombie, Leslie; Jenkins, Peter; Mitchard, D. A.

doi:10.1039/p19750001081

Cited by 14 publications

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“…The methylester of butadietlecarboxylic acid (CH,=C= CHCOOCH,) was synthesized from the acid and diazomethane (24). The acid was prepared from allene, n-butyllithium, and CO, (25).…”

Section: Trifluoroacetic-trans-crotonic Anhydride ( C F -C O G Co-cmentioning

confidence: 99%

Isomeric and tautomeric [C₄H₄O]^+• ions; their thermochemistry and collisionally induced fragmentation characteristics

Burgers¹,

Holmes²,

Lossing³

et al. 1982

Can. J. Chem.

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Ionic heats of formation and collisional activation (CA) mass spectra for fifteen isomeric or tautomeric [C4H4O]+• ions are described. Twelve of these species can be characterised by means of their CA mass spectra alone. The relative thermodynamic stabilities of keto–enol tautomers and the ease of interconversion of some ions are discussed. It is emphasised that CA spectra alone (i.e. in the absence of other information, such as heat of formation, etc.) may not easily be correlated with the appropriate ion structures.

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“…The methylester of butadietlecarboxylic acid (CH,=C= CHCOOCH,) was synthesized from the acid and diazomethane (24). The acid was prepared from allene, n-butyllithium, and CO, (25).…”

Section: Trifluoroacetic-trans-crotonic Anhydride ( C F -C O G Co-cmentioning

confidence: 99%

Isomeric and tautomeric [C₄H₄O]^+• ions; their thermochemistry and collisionally induced fragmentation characteristics

Burgers¹,

Holmes²,

Lossing³

et al. 1982

Can. J. Chem.

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“…Earlier studies reported in the literature indicated that the selectivity of supported metal catalysts among different chemo-, regio-, and stereoselective hydrogenation products is generally low for this challenging allene hydrogenation reaction [5–10]. For example, palladium on alumina catalyst, which was synthesized by the hydrothermal method, converted allenes into alkenes, with a relatively low and time-dependent selectivity [9,10].…”

Section: Introductionmentioning

confidence: 99%

“…Selective mono-hydrogenation of substituted allenes could produce four different stereoisomeric alkenes depending on the regio- and stereoselective addition of hydrogen, as shown in Scheme 1. Most heterogeneous catalysts, including supported Pd, Pt, Rh, and Ir, produced cis -1,2-hydrogenation products as major products, with maximum yields ranging from 70% to 98%, that are highly dependent on the reaction time and hydrogen pressure [5,6,11]. Most of these catalysts produced full hydrogenation products as major products after an extended reaction time.…”

Section: Introductionmentioning

confidence: 99%

Alkanethiolate-Capped Palladium Nanoparticles for Regio- and Stereoselective Hydrogenation of Allenes

Chen

Shon

2018

Catalysts

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Colloidal Pd nanoparticles capped with octanethiolate ligands have previously shown an excellent selectivity toward the mono-hydrogenation of both isolated and conjugated dienes to internal alkenes. This paper reports an efficient stereoselective mono-hydrogenation of cumulated dienes (allenes) to either Z or E olefinic isomers, depending on the substitution pattern around C=C bonds. Kinetic studies indicate that the reaction progresses through the hydrogenation of less hindered C=C bonds to produce internal Z olefinic isomers. In the cases of di-substitued olefinic products, this initial hydrogenation step is followed by the subsequent isomerization of Z to E isomers. In contrast, the slow isomerization of Z to E isomers for tri-substituted olefinic products results in the preservation of Z stereochemistry. The high selectivity of Pd nanoparticles averting an additional hydrogenation is steered from the controlled electronic and geometric properties of the Pd surface, which are the result of thiolate-induced partial poisoning and surface crowding, respectively. The high activity of colloidal Pd nanoparticle catalysts allows the reactions to be completed at room temperature and atmospheric pressure.

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“…The catalytic hydrogenation of allenes is particularly responsive to the `catalyst hindrance' presented by dierent orientations of the allene to the hydrogen adsorbed on the catalyst surface. 3,4 Indeed such hindrance eects can provide a means of converting molecular dissymmetry into centrodissymmetry, hence allowing an experimental determination of the absolute con®guration of an optically active allene. 5 The hydrogenation of 1-(2-methylpropenylidene)-7-bicyclo-[4.1.0]heptane 1 over Pt was followed using GLC `snapshot analysis' (Graph 1).…”

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confidence: 99%

The Heterogeneous Catalytic Hydrogenation of Cumulated Allene-cyclopropanes: 1-(2′-Methylpropenylidene)-7-bicyclo[4.1.0]heptane

Crombie¹,

Fernando²

1998

J. Chem. Res.

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Heterogeneous catalytic hydrogenation of allenes over supported palladium: selectivity, stereoselectivity, and regioselectivity

Cited by 14 publications

References 0 publications

Isomeric and tautomeric [C₄H₄O]^+• ions; their thermochemistry and collisionally induced fragmentation characteristics

Isomeric and tautomeric [C₄H₄O]^+• ions; their thermochemistry and collisionally induced fragmentation characteristics

Alkanethiolate-Capped Palladium Nanoparticles for Regio- and Stereoselective Hydrogenation of Allenes

The Heterogeneous Catalytic Hydrogenation of Cumulated Allene-cyclopropanes: 1-(2′-Methylpropenylidene)-7-bicyclo[4.1.0]heptane

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Heterogeneous catalytic hydrogenation of allenes over supported palladium: selectivity, stereoselectivity, and regioselectivity

Cited by 14 publications

References 0 publications

Isomeric and tautomeric [C4H4O]+• ions; their thermochemistry and collisionally induced fragmentation characteristics

Isomeric and tautomeric [C4H4O]+• ions; their thermochemistry and collisionally induced fragmentation characteristics

Alkanethiolate-Capped Palladium Nanoparticles for Regio- and Stereoselective Hydrogenation of Allenes

The Heterogeneous Catalytic Hydrogenation of Cumulated Allene-cyclopropanes: 1-(2′-Methylpropenylidene)-7-bicyclo[4.1.0]heptane

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Isomeric and tautomeric [C₄H₄O]^+• ions; their thermochemistry and collisionally induced fragmentation characteristics

Isomeric and tautomeric [C₄H₄O]^+• ions; their thermochemistry and collisionally induced fragmentation characteristics