Hydrogen transfer from formic acid to alkynes catalyzed by a diruthenium complex

2001 ◽  
Vol 79 (5-6) ◽  
pp. 915-921 ◽  
Author(s):  
Yuan Gao ◽  
Michael C Jennings ◽  
Richard J Puddephatt
Keyword(s):  
Carbon Dioxide ◽  
Formic Acid ◽  
Hydrogen Transfer ◽  
Hydrogen Donor ◽  
Transfer Hydrogenation ◽  
Stable Complex ◽  
Terminal Alkynes ◽  
Hydrogenation Catalysis ◽  
Diruthenium Complex ◽  
Electron Withdrawing Substituents

The diruthenium(0) complex [Ru2(µ-CO)(CO)4(µ-dppm)2] (1) (dppm = Ph2PCH2PPh2), is a catalyst for the transfer hydrogenation, using formic acid as hydrogen donor, of the alkynes PhCºCPh, PhCºCMe, EtCºCEt, and PrCºCPr but not of the terminal alkynes HCºCH, PhCºCH, BuCºCH, or the alkynes containing one or two electron-withdrawing substituents PhCºCCO2Me and MeO2CCtriple bondCCO2Me. In the successful reactions, the formic acid is first decomposed to carbon dioxide and hydrogen, which then hydrogenates the alkynes in a slower reaction. In the unsuccessful reactions, the decomposition of formic acid is strongly retarded by the alkyne. In the case with the alkyne PhCºCH, it is shown that the alkyne reacts with protonated 1 to give first [Ru2(µ-CPh=CH2)(CO)4(µ-dppm)2][HCO2], which then isomerizes to give the catalytically inactive, stable complex [Ru2(µ-CH=CHPh)(CO)4(µ-dppm)2][HCO2]. This complex has been structurally characterized and both of the µ-styrenyl complexes are shown to be fluxional in solution.Key words: ruthenium, hydrogenation, catalysis, binuclear..

scholarly journals Insight into catalyst speciation and hydrogen co-evolution during enantioselective formic acid-driven transfer hydrogenation with bifunctional ruthenium complexes from multi-technique operando reaction monitoring

2019 ◽  
Vol 220 ◽  
pp. 45-57 ◽  
Author(s):  
Daniel B. G. Berry ◽  
Anna Codina ◽  
Ian Clegg ◽  
Catherine L. Lyall ◽  
John P. Lowe ◽  
...  
Keyword(s):  
Formic Acid ◽  
Maximum Rate ◽  
Hydrogen Transfer ◽  
Ruthenium Complexes ◽  
Transfer Hydrogenation ◽  
Reaction Monitoring ◽  
Optimal Conditions ◽  
Insight Into

Operando spectroscopy shows a transition from dehydrogenation to hydrogen transfer during the reaction, and allows measuring optimal conditions for maximum rate and efficiency.

Magnesium Aluminate Supported Cu Catalyst for Selective Transfer Hydrogenation of Biomass Derived Furfural to Furfuryl Alcohol with Formic Acid as Hydrogen Donor

2019 ◽  
Vol 4 (1) ◽  
pp. 145-151 ◽  
Author(s):  
Peddinti Nagaiah ◽  
Paleti Gidyonu ◽  
Muppala Ashokraju ◽  
Madduluri Venkata Rao ◽  
Prathap Challa ◽  
...  
Keyword(s):  
Formic Acid ◽  
Furfuryl Alcohol ◽  
Hydrogen Donor ◽  
Transfer Hydrogenation ◽  
Magnesium Aluminate ◽  
Selective Transfer ◽  
Cu Catalyst

scholarly journals Highly Selective Vapor and Liquid Phase Transfer Hydrogenation of Diaryl and Polycyclic Ketones with Secondary Alcohols in the Presence of Magnesium Oxide as Catalyst

Catalysts ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 574
Author(s):  
Marek Gliński ◽  
Anna Markowska ◽  
Laura Wrońska ◽  
Anna Jerzak ◽  
Magdalena Tarkowska
Keyword(s):  
Liquid Phase ◽  
Hydrogen Transfer ◽  
Phase Transfer ◽  
Scale Up ◽  
Hydrogen Donor ◽  
Transfer Hydrogenation ◽  
Side Reactions ◽  
Ortho Position ◽  
Donor Acceptor ◽  
Phenyl Ketone

MgO has been shown to catalyze an almost quantitative hydrogen transfer from 2-octanol as the hydrogen donor to benzophenone to form benzhydrol, a useful intermediate product in the pharmaceutical industry. The hydrogen transfer from a series of alcohols to the carbonyl group of benzophenone, its ten derivatives, four polycyclic ketones, and 2-naphthyl phenyl ketone was carried out in liquid (LP) or vapor phase (VP). The dependence of reactivity on the structure of the hydrogen donor, reaction temperature, donor-acceptor ratio, amount of catalyst, and the type and position of substituents has been established. For both reaction modes, optimal conditions for selective synthesis of the alcohols were determined and side reactions were investigated. The results indicate that the reactivity of the ketone is suppressed by the presence of a methyl substituent in the ortho position to a much greater extent in LP mode. A scale-up was demonstrated in the liquid phase mode.

Cobalt-catalysed transfer hydrogenation of quinolines and related heterocycles using formic acid under mild conditions

2017 ◽  
Vol 7 (10) ◽  
pp. 1981-1985 ◽  
Author(s):  
Jose R. Cabrero-Antonino ◽  
Rosa Adam ◽  
Kathrin Junge ◽  
Ralf Jackstell ◽  
Matthias Beller
Keyword(s):  
Formic Acid ◽  
Noble Metal ◽  
Hydrogen Donor ◽  
Transfer Hydrogenation ◽  
Time Transfer ◽  
Mild Conditions ◽  
Mild Reduction ◽  
First Time

For the first time, transfer hydrogenation of quinolines and related heterocycles is performed with a non-noble metal based catalyst. [Co(BF4)2·6H2O] in combination with phosphine L1 catalyses selectively, the mild reduction of N-heteroarenes using formic acid as hydrogen donor.

scholarly journals Chemoselective Transfer Hydrogenation of α,β-Unsaturated Ketones Catalyzed by Iridium Complexes

SynOpen ◽  
2021 ◽  
Vol 05 (01) ◽  
pp. 36-42
Author(s):  
Renshi Luo ◽  
Yanping Xia ◽  
Lu Ouyang ◽  
Jianhua Liao ◽  
Xiao Yang
Keyword(s):  
Formic Acid ◽  
Functional Groups ◽  
Organic Solvents ◽  
Mixed Solvents ◽  
Transfer Hydrogenation ◽  
Scale Transformation ◽  
Iridium Complexes ◽  
Practical Application ◽  
Unsaturated Ketones ◽  
Electron Withdrawing Substituents

AbstractEfficient chemoselective transfer hydrogenation of the C=C bond of α,β-unsaturated ketones has been developed, using the iridium complexes containing pyridine-imidazolidinyl ligands as catalysts and formic acid as a hydrogen source. In comparison with organic solvents or H2O as solvent, the mixed solvents of H2O and MeOH are critical for a high catalytic chemoselective transformation. This chemoselective transfer hydrogenation can be carried out in air, which is operationally simple, allowing a wide variety of α,β-unsaturated substrates with different functional groups (electron-donating and electron-withdrawing substituents) leading to chemoselective transfer hydrogenation in excellent yields. The practical application of this protocol is demonstrated by a gram-scale transformation.

Rhodium-Catalyzed anti and syn Enantio- and Diastereoselective Transfer Hydrogenation of α-Amino β-Keto Ester Hydrochlorides through Dynamic Kinetic Resolution

Synthesis ◽  
2016 ◽  
Vol 48 (19) ◽  
pp. 3357-3363 ◽  
Author(s):  
Quentin Llopis ◽  
Charlène Férard ◽  
Gérard Guillamot ◽  
Phannarath Phansavath ◽  
Virginie Ratovelomanana-Vidal
Keyword(s):  
Formic Acid ◽  
Kinetic Resolution ◽  
Amino Alcohols ◽  
Hydrogen Donor ◽  
Transfer Hydrogenation ◽  
Asymmetric Transfer Hydrogenation ◽  
Dynamic Kinetic Resolution ◽  
Keto Ester ◽  
Catalytic Asymmetric ◽  
Donor Source

A mild catalytic asymmetric transfer hydrogenation of a series of α-amino β-keto ester hydrochlorides catalyzed by a rhodium(III) complex is reported. The use of the formic acid/triethylamine system as the hydrogen donor source provided the corresponding anti and syn amino alcohols with complete conversions, fair diastereoselectivities (up to 97:3 dr), and high enantioselectivities (ee up to >99%).

Unprecedented catalytic performance in amine syntheses via Pd/g-C3N4 catalyst-assisted transfer hydrogenation

2018 ◽  
Vol 20 (9) ◽  
pp. 2038-2046 ◽  
Author(s):  
Xingliang Xu ◽  
Jiajun Luo ◽  
Liping Li ◽  
Dan Zhang ◽  
Yan Wang ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Formic Acid ◽  
Catalytic Performance ◽  
Nitro Compounds ◽  
Hydrogen Donor ◽  
Transfer Hydrogenation ◽  
Secondary Amines ◽  
Primary And Secondary Amines

A Pd/g-C3N4 catalyst exhibited a superb performance in the transfer hydrogenation of nitro compounds to generate their corresponding primary and secondary amines with formic acid as the hydrogen donor in aqueous solution.

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