Evidence for Direct Hydride Delivery from Formic Acid in Transfer Hydrogenation

Yu, Jin‐Quan; Spencer, Jonathan B.

doi:10.1002/(sici)1521-3765(19990802)5:8<2237::aid-chem2237>3.0.co;2-o

Cited by 27 publications

(17 citation statements)

References 13 publications

(16 reference statements)

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“…Given the fact that palladium is well-known to react with acetic during the isomerization of a cis enol ether (Figure 4c). 8 The results showed that the deuterium from the formyl position was incorporated exclusively into the electron-deficient center of the double bond, while the identities of the two hydrogens were not scrambled during the transfer hydrogenation, indicating the formyl hydrogen is more reactive than the carboxyl hydrogen. It was proposed that the isomerization reaction proceed via an intermolecular hydride transfer mechanism with a sixmembered-ring intermediate, similar to the Meerwein− Ponndorf−Verley (MPV) mechanism (Figure 4d).…”

Section: Reaction Mechanisms Of Cth With Famentioning

confidence: 99%

“…In transfer hydrogenation, FA that contains active hydrogen is used to replace molecular hydrogen. Different from the traditional hydrogenation, the first step of transfer hydrogenation is the chemisorption of active hydrogen on a catalyst, which was proposed to occur via two reaction mechanisms: 8 (1) the dihydrido metal species formed by the loss of carbon dioxide from metal formato hydrido complex leading to hydrogen transfer from FA to the metal surface (Figure 3a); (2) metal diformate as a key intermediate, which could decompose to generate the dihydrido metal species (Figure 3b).…”

Section: Reaction Mechanisms Of Cth With Famentioning

confidence: 99%

“…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%

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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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Section: Reaction Mechanisms Of Cth With Famentioning

confidence: 99%

Section: Reaction Mechanisms Of Cth With Famentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2021

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“…A variety of hydrogen donors have been used, including inorganic salts (borohydrides [22][23][24], phosphinates [25]) organic salts (formic acid and its salts [26][27][28], hydrazine·HCl [29,30]), alcohols (butan-2-ol [31], propan-2-ol [32,33]), or proaromatic compounds. Alternatively, CO [34,35] (water-gas shift reaction), zero-valent metal [36][37][38][39] and bimetallic mixtures [40,41] can mediate H 2 O hydrolytic reduction.…”

Section: Introductionmentioning

confidence: 99%

Catalytic hyrodechlorination of chlorophenols in aqueous solution under mild conditions

Roy

Wai

Yuan

et al. 2004

Applied Catalysis A: General

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“…Horiuti and Polanyi have introduced a mechanism for CH of alkenes in the presence of heterogeneous catalysts. − Moreover, several mechanisms have been reported for CTH in alkenes. ,− These mechanisms are common to all types of alkenes.…”

Section: Introductionmentioning

confidence: 99%

A Simple Method for Safe Determination of the Activity of Palladium on Activated Carbon Catalysts in the Hydrogenation of Cinnamic Acid to Hydrocinnamic Acid

Mousavi

Nazari

Keshavarz

et al. 2020

Ind. Eng. Chem. Res.

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A simple method was introduced to determine the activities of activated carbon-supported palladium (Pd/AC) catalysts in the hydrogenation of cinnamic acid (CA). Catalytic transfer hydrogenation (CTH) of CA to hydrocinnamic acid (HCA) is a suitable reaction for this purpose. In order to detect the reaction completion, the simple Bayer's test is also a good alternative for the costly device test, for example, GC and HPLC. The ability of this method for accurate measurement of the catalyst activity is proven by comparing its results with data obtained from the catalytic hydrogenation (CH) reaction of CA to HCA. Four commercial 10% Pd/AC catalysts were used in which their characterizations are determined. The reliability of correlation between the obtained activities from catalysts in two CH and CTH reactions is confirmed by high and low values of the coefficient of determination (R 2 = 0.9895) and standard error (s = 2.84), respectively. It is indicated that there are some similarities between the mechanisms of these two reactions. Since their kinetics are very similar, the rates of both catalyzed reactions are zero-order. Here, we show that this method can measure the activity of Pd/AC catalysts in CH of CA as well as investigate the possible use of this method for the hydrogenation of other alkenes.

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Evidence for Direct Hydride Delivery from Formic Acid in Transfer Hydrogenation

Cited by 27 publications

References 13 publications

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

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

Catalytic hyrodechlorination of chlorophenols in aqueous solution under mild conditions

A Simple Method for Safe Determination of the Activity of Palladium on Activated Carbon Catalysts in the Hydrogenation of Cinnamic Acid to Hydrocinnamic Acid

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