Heterogeneous transfer hydrogenation involves pairwise hydrogen transfer from the same position of two molecules of formic acid

Yu, Jin‐Quan; Spencer, Jonathan B.

doi:10.1039/a803809k

Cited by 22 publications

(20 citation statements)

References 20 publications

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“…These results are in agreement with a rate determining step involving a CTH mechanism. Spencer et al 40 have also concluded that the hydrogenation of unsaturated C-C bonds using FAc and Pd/C as catalyst operates via a CTH mechanism. In their case an alkyne (methyl phenylpropiolate) was hydrogenated to the corresponding cisalkene using trimethylamine as solvent.…”

Section: Experimental Evidences Of Cth Mechanismmentioning

confidence: 99%

“…In their case an alkyne (methyl phenylpropiolate) was hydrogenated to the corresponding cisalkene using trimethylamine as solvent. Besides, Spencer et al 40 also demonstrated that the hydrogen transfer occurs via two palladium-diformate species from two different FAc molecules: the two formyl hydrogens from the two diformate species concertedly hydrogenate the double bond. The acid proton was not involved in the hydrogenation.…”

Section: Experimental Evidences Of Cth Mechanismmentioning

confidence: 99%

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Catalytic transfer hydrogenation of maleic acid with stoichiometric amounts of formic acid in aqueous phase: paving the way for more sustainable succinic acid production

et al. 2020

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Section: Experimental Evidences Of Cth Mechanismmentioning

confidence: 99%

Section: Experimental Evidences Of Cth Mechanismmentioning

confidence: 99%

Catalytic transfer hydrogenation of maleic acid with stoichiometric amounts of formic acid in aqueous phase: paving the way for more sustainable succinic acid production

et al. 2020

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“…For instance, hydrogen is transferred from FA to the substrate through various mechanistic pathways, such as intermolecular hydride transfer. 7,8 Furthermore, the competitive adsorption of FA with reactants and reaction intermediates could markedly influence the product distribution. 9 Homogeneous CTH with FA plays an increasing role in the development of selective hydrogenation and may be one of the most extensively studied type of homogeneously catalyzed reactions.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Catalytic Transfer Hydrogenation with Formic Acid over Heterogeneous Transition Metal Catalysts

et al. 2021

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Transition-metal-catalyzed transfer hydrogenation with an in situ hydrogen donor has received a great deal of attention from both academia and industry as an alternative to the traditional high-pressure-hydrogen process, owing to its better efficiency, atom economy, and sustainability features. Hydrogen stored in the chemical bonds of formic acid (FA), a promising hydrogen storage compound that could be derived from biomass or reduction of CO2, can be extracted selectively and used for diverse catalytic transformations. This Review summarizes and compares recent progress in catalytic transfer hydrogenation (CTH) via heterogeneous hydrogen transfer from FA. Transformations of biomass-derived platform chemicals (e.g., aromatic units, C5 and C6 sugars, furans, glycerol, fatty acids, levulinic acid (LA)), nitrogen-containing compounds (e.g., nitroarenes, quinolines), and organochlorinated compounds via transfer hydrogenation, hydrogenolysis, and hydrodechlorination (HDC) are outlined. Synthesis strategies of the heterogeneous metal catalysts (e.g., metal and support type, metal–support interaction, single-atom, alloy effect, and confinement effect) and optimization of the reaction conditions (e.g., temperature, solvents, additives, and FA dosages) for enhancing the catalytic activity and regulating the product distribution are presented. Structure–activity relationships based on both dehydrogenation and hydrogenation of metal catalysts as well as the mechanistic interpretation of CTH with FA are also highlighted. Finally, current challenges and outlook for the future development of the field are discussed.

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“…[15] For heterogeneous transfer hydrogenation an alternative mechanism was suggested on the basis of labeling studies that involved palladium diformate (3) as a key intermediate (Scheme 2). [16] This intermediate could collapse to form the dihydrido metal species 4, which then reacts with the unsaturated compound. The surface-bound metal center represented by the dihydrido metal species 4 should be equivalent to that generated from hydrogen gas with the catalyst, and should therefore have the same reactivity.…”

Section: Introductionmentioning

confidence: 99%

Evidence for Direct Hydride Delivery from Formic Acid in Transfer Hydrogenation

Spencer

1999

Chemistry - A European Journal

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The regioselectivity of hydrometalation in transfer hydrogenation was investigated by tracing the fate of the deuterium label in both the formyl and carboxyl positions of formic acid during the isomerization of a cis enol ether. The deuterium from the formyl position is incorporated exclusively into the electron-deficient center of the double bond; this indicates that hydride attack occurs during transfer hydrogenation. The fact that the formyl hydrogen is more reactive than the carboxyl hydrogen suggests that the identities of the two hydrogens are not scrambled during transfer hydrogenation. We propose that the delivery of the formyl hydrogen atom is concerted with decarboxylation rather than proceeding through the formation of a metal dihydrido species.

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Heterogeneous transfer hydrogenation involves pairwise hydrogen transfer from the same position of two molecules of formic acid

Cited by 22 publications

References 20 publications

Catalytic transfer hydrogenation of maleic acid with stoichiometric amounts of formic acid in aqueous phase: paving the way for more sustainable succinic acid production

Catalytic transfer hydrogenation of maleic acid with stoichiometric amounts of formic acid in aqueous phase: paving the way for more sustainable succinic acid production

Recent Advances in Catalytic Transfer Hydrogenation with Formic Acid over Heterogeneous Transition Metal Catalysts

Evidence for Direct Hydride Delivery from Formic Acid in Transfer Hydrogenation

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