Arene Hydrogen Research Articles

Colloidal Bimetallic RuNi Particles and their Behaviour in Catalytic Quinoline Hydrogenation.

Colloidal metal nanoparticles exhibit interesting catalytic properties for the hydrogenation of (hetero)arenes. Catalysts based on precious metals, such as Ru and Rh, promote this reaction efficiently under mild reaction conditions. In contrast, heterogeneous catalysts based on earth-abundant metals can selectively hydrogenate (hetero)arenes but require harsher reaction conditions. Bimetallic catalysts that combine precious and earth-abundant metals are interesting materials to mitigate the drawbacks of each component. To this end, RuNi nanoparticles bearing a phosphine ligand were prepared through the decomposition of [Ru(η4-C8H12)(η6-C8H10)] and [Ni(η4-C8H12)2] by H2 at 85 °C. Wide angle X-ray scattering confirmed a bimetallic segregated structure, with Ni predominantly on the surface. Spectroscopic analyses revealed that the phosphine ligand coordinated to the surface of both metals, suggesting, as well, a partial Ni shell covering the Ru core. The RuNi-based nanomaterials were used as catalysts in the hydrogenation of quinoline to assess the impact of the metallic composition and of the stabilizing agent on their catalytic performance.

Hydrogenation of Arenes at Room Temperature under 1 atm of Hydrogen Gas by Rh-Pd/C or Rh-Pt

Hydrogenation of Arenes at Room Temperature under 1 atm of Hydrogen Gas by Rh-Pd/C or Rh-Pt

Hydrogenation of inert aromatic compounds under mild conditions catalyzed by confined trimetal sites in porous metal silicate materials

Complete hydrogenation of aromatic compounds is an important subject in various industry fields. However, due to the high stabilization energy of aromatic compounds resulting from their high aromaticity and non-polarity, the hydrogenation reaction is usually performed under harsh reaction conditions in the presence of noble metal-based catalysts. We report herein a porous metal silicate (PMS) material PMS-58, which consists of Cu, Ce and Co trimetal active sites, demonstrating high catalytic activity and selectivity in hydrogenating of a series of aromatic compounds under mild conditions (60 °C and 0.5 MPa H2). PMS-58 is superior to the previously reported non-noble metal-based catalysts and could be favorably compared to noble metal-based catalysts. The unique catalytic properties of PMS-58 are derived from the synergistic work of trimetal sites with Ce species serving as strong Lewis acid sites for dissociation of dihydrogen, Co species stabilizing Cu(I) species, and Cu(I) species playing a crucial role in activating aromatic rings. Therefore, this work provides a new approach in developing highly efficient non-noble metal catalysts for complete hydrogenation of arenes under mild conditions, which could be applied in removal of aromatic compounds in petroleum products.

Mechanism of Alkaline Earth Metal Amide Catalyzed Hydrogenation of Challenging Alkenes and Arenes.

Recently, bulky alkaline earth (Ae=Mg, Ca, Sr, Ba) metal amide complexes AeN"2 (N"=N[Si(iPr)3]2) are shown to be active for catalyzing the hydrogenation of unactivated alkenes and arenes, presumably via the monomer N"AeH as catalyst. In sharp contrast, our extensive DFT calculations disclose that the double Ae-H-Ae bridged dimer (N"AeH)2 is kinetically more favorable in catalytic hydrogenation with H2, although rate-limited by the initial hydrogenolysis of AeN"2 to form the monomer N"AeH.

Switchable and Chemoselective Arene Hydrogenation for Efficient Late Stage Applications.

The incorporation of three-dimensional structures into drug molecules has demonstrated significant improvements in clinical success. Late-stage saturation of drug molecules provides a direct pathway for this transformation. However, achieving selective and controllable reduction of aromatic rings remains challenging, particularly when multiple aromatic rings coexist. Herein, we present the switchable and chemoselective hydrogenation of benzene and pyridine rings. The utility of the protocol has been comprehensively investigated in diversified substrates with the assistance of a fragment-screening technique. This approach provides convenient access to a diverse array of cyclohexane and piperidine compounds, prevalent in various bioactive molecules and drugs. Furthermore, it discloses promising avenues for applications in the late-stage switchable saturation of drugs, facilitating an increase in the fraction of sp3-carbons which holds the potential to enhance the medicinal properties of drugs.

Scalable and Selective Electrochemical Hydrogenation of Polycyclic Arenes.

The reduction of aromatic compounds constitutes a fundamental and ongoing area of investigation. The selective reduction of polycyclic aromatic compounds to give either fully or partially reduced products remains a challenge, especially in applications to complex molecules at scale. Herein, we present a selective electrochemical hydrogenation of polycyclic arenes conducted under mild conditions. A noteworthy achievement of this approach is the ability to finely control both the complete and partial reduction of specific aromatic rings within polycyclic arenes by judiciously varying the reaction solvents. Mechanistic investigations elucidate the pivotal role played by in situ proton generation and interface regulation in governing reaction selectivity. The reductive electrochemical conditions show a very high level of functional-group tolerance. Furthermore, this methodology represents an easily scalable reduction (demonstrated by the reduction of 1 kg scale starting material) using electrochemical flow chemistry to give key intermediates for the synthesis of specific drugs.

Scalable and Selective Electrochemical Hydrogenation of Polycyclic Arenes

Scalable and Selective Electrochemical Hydrogenation of Polycyclic Arenes

Pd/C-Catalyzed Stereoselective Arene Hydrogenation of Benzocyclobutenes Enabled by π-Bond Localization.

We developed here a Pd/C-catalyzed diastereoselective cis-hydrogenation of benzocyclobutene derivatives under mild conditions to deliver an array of bicyclo[4.2.0]octane scaffolds with up to five stereocenters. The π-bond localization enabled hydrogenation of the arene moiety to occur even at room temperature under 1 atm of a H2 atmosphere.

Organic Acid‐Assisted Preparation of Hydroxyapatite‐supported Ni Catalysts for Arene Hydrogenation

Developing non‐noble metal catalysts that can efficiently and selectively hydrogenate arenes remains a significant challenge. In this study, we developed efficient Ni catalysts for the arene hydrogenation based on an organic acid‐regulated impregnation strategy. These easily accessible Ni catalysts demonstrated exceptional efficiency, selectivity, reusability, and good substrate compatibility. The influence of carbon chain lengths and side‐chain hydroxyl or amino groups on dicarboxylic acids used in the catalyst preparation was comprehensively investigated. Characterizations and kinetic studies demonstrated the influence of organic acids on the size of Ni nanoparticles, the proportion of metallic nickel, and the strength of surface acidity. These factors influenced the activation of arene and hydrogen, thereby affecting the hydrogenative activity. Notably, hydroxyapatite‐supported Ni catalyst, assisted by tartaric acid (Ni‐TA/HAP) with an appropriate tartaric acid‐to‐nickel ratio, resulted in relatively smaller Ni nanoparticles, an increased proportion of Ni0, and more acidic sites, thereby exhibiting the best hydrogenation performance.

Arene Reduction by Rh/Pd or Rh/Pt under 1 atm Hydrogen Gas and Room Temperature.

Current methods for arene hydrogenation generally need either harsh reaction conditions or complex catalyst preparation. Here we describe a mild and convenient protocol that only utilizes commercially available catalysts. Using [Rh(nbd)Cl]2 and Pd/C together as catalysts, arenes bearing various functional groups can be hydrogenated under 1 atm of H2 at room temperature. This arene hydrogenation can also be achieved using catalysts of [Rh(cod)Cl]2 and PtO2, thus avoiding glovebox manipulations and simplifying the reaction procedure.

Transfer Hydrogenation of Vinyl Arenes and Aryl Acetylenes with Ammonia Borane Catalyzed by Schiff Base Cobalt(II) Complexes.

A series of bench-stable Co(II) complexes containing hydrazone Schiff base ligands were evaluated in terms of their activity and selectivity in carbon-carbon multiple bond transfer hydrogenation. These cobalt complexes, especially a Co(II) precatalyst bearing pyridine-2-yl-N(Me)N=C-(1-methyl)imidazole-2-yl ligand, activated by LiHBEt3, were successfully used in the transfer hydrogenation of substituted styrenes and phenylacetylenes with ammonia borane as a hydrogen source. Key advantages of the reported catalytic system include mild reaction conditions, high selectivity and tolerance to functional groups of substrates.

Colloidal ruthenium catalysts for selective quinaldine hydrogenation: Ligand and solvent effects.

Colloidal Ru nanoparticles (NP) display interesting catalytic properties for the hydrogenation of (hetero)arenes as they proceed efficiently in mild reaction conditions. In this work, a series of Ru based materials was used in order to selectively hydrogenate quinaldine and assess the impact of the stabilizing agent on their catalytic performances. Ru nanoparticles stabilized with polyvinylpyrrolidone (PVP) and 1-adamantanecarboxylic acid (AdCOOH) allowed to obtain 5,6,7,8-tetrahydroquinaldine with a remarkable selectivity in mild reaction conditions by choosing the suitable solvent. The presence of a carboxylate ligand on the surface of the Ru NP led to an increase in the activity when compared to Ru/PVP catalyst. The stabilizing agent had also an impact on the selectivity, as carboxylate ligand modified catalysts promoted the selectivity towards 1,2,3,4-tetrahydroquinaldine, with bulky carboxylate displaying the highest ones.

Synthesis of diamondoids through hydrogenation of adamantane-annulated arenes

Abstract Diamondoids are cage-shaped saturated hydrocarbons whose carbon scaffolds are substructures of diamond. Despite their potential application, the availability of diamondoids has been significantly limited due mainly to the difficulty in synthesis. Herein, we report a new synthetic methodology for diamondoids. It was found that adamantane-annulated arenes, which can be synthesized by our recently developed method, can be transformed to saturated hydrocarbons by catalytic hydrogenation of arene moieties. The thus-obtained hydrocarbons are unnatural diamondoids, which are otherwise difficult toobtaine. The structural analysis and DFT calculation of the reaction mechanism were also performed to initiate exploration of the untapped synthetic chemistry of diamondoids.

Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO2 -Responsive Support.

Ruthenium nanoparticles (NPs) immobilized on an amine-functionalized polymer-grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full hydrogenation of benzofuran and quinoline derivatives is achieved under pure H2 , introducing CO2 into the H2 gas phase leads to an effective shutdown of the arene hydrogenation while preserving the activity for the hydrogenation of the heteroaromatic part. The selectivity switch originates from the generation of ammonium formate species on the surface of the materials by catalytic hydrogenation of CO2 . The CO2 hydrogenation is fully reversible, resulting in a robust and rapid switch between the two states of the catalyst adapting its performance in response to the feed gas composition. A variety of benzofuran and quinoline derivatives were hydrogenated to fully or partially saturated products in high selectivity and yields simply by altering the composition of the feed gas from H2 to H2 /CO2 . The adaptive catalytic system thus provides controlled access to valuable products using a single catalyst rather than two specific and distinct catalysts with static reactivity.

Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO2‐Responsive Support

AbstractRuthenium nanoparticles (NPs) immobilized on an amine‐functionalized polymer‐grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full hydrogenation of benzofuran and quinoline derivatives is achieved under pure H2, introducing CO2 into the H2 gas phase leads to an effective shutdown of the arene hydrogenation while preserving the activity for the hydrogenation of the heteroaromatic part. The selectivity switch originates from the generation of ammonium formate species on the surface of the materials by catalytic hydrogenation of CO2. The CO2 hydrogenation is fully reversible, resulting in a robust and rapid switch between the two states of the catalyst adapting its performance in response to the feed gas composition. A variety of benzofuran and quinoline derivatives were hydrogenated to fully or partially saturated products in high selectivity and yields simply by altering the composition of the feed gas from H2 to H2/CO2. The adaptive catalytic system thus provides controlled access to valuable products using a single catalyst rather than two specific and distinct catalysts with static reactivity.

Hydrogenation of Arenes by Cobalt Nanoparticles Supported on Biomass-Derived Carbons

Hydrogenation of Arenes by Cobalt Nanoparticles Supported on Biomass-Derived Carbons

Arene Insertion with Pincer-Supported Molybdenum-Hydrides: Determination of Site Selectivity, Relative Rates, and Arene Complex Formation.

The synthesis of phosphino(oxazoline)pyridine-supported molybdenum(0) cycloocta-1,5-diene complexes is described. Exposure of these complexes to dihydrogen in the presence of an arene resulted in insertion of the substrate into the molybdenum hydride bond and afforded the corresponding molybdenum cyclohexadienyl hydrides. For mono- and disubstituted arenes, the site selectivity for insertion of the most substituted bond increases with increasing size of the substituent from methyl to ethyl, iso-propyl, and tert-butyl. In contrast, 1,3,5-trisubstituted arenes underwent insertion with exclusive site selectivity. Relative rates of insertion were determined by competition experiments and established faster insertions for electron-rich arenes. Introduction of electron-withdrawing trifluoromethyl groups on the arene resulted in decreased relative rates of insertion and an increased rate for H2 reductive elimination, favoring formation of the corresponding molybdenum η6-arene complex. Studies on the reductive elimination of the cyclohexadienyl ligand with the hydride enabled the synthesis of an enantioenriched cyclohexa-1,3-diene. This study provides new insights into the ligand requirements for catalytic arene hydrogenation and a new strategy for selective arene reduction.

Earth-Abundant Heterogeneous Cobalt Catalyst for Selective Ring Hydrogenation of (Hetero)arenes and Gram-Scale Synthesis of Pharmaceutical Intermediates

Earth-Abundant Heterogeneous Cobalt Catalyst for Selective Ring Hydrogenation of (Hetero)arenes and Gram-Scale Synthesis of Pharmaceutical Intermediates

Nanoscale Ni-NiO-ZnO Heterojunctions for Switchable Dehydrogenation and Hydrogenation through Modulation of Active Sites.

Catalysts consisting of metal-metal hydroxide/oxide interfaces are highly in demand for advanced catalytic applications as their multicomponent active sites will enable different reactions to occur in close proximity through synergistic cooperation when a single component fails to promote it. To address this, herein we disclosed a simple, scalable, and affordable method for synthesizing catalysts consisting of nanoscale nickel-nickel oxide-zinc oxide (Ni-NiO-ZnO) heterojunctions by a combination of complexation and pyrolytic reduction. The modulation of active sites of catalysts was achieved by varying the reaction conditions of pyrolysis, controlling the growth, and inhibiting the interlayer interaction and Ostwald ripening through the efficient use of coordinated acetate and amide moieties of Zn-Ni materials (ZN-O), produced by the reaction between hydrazine hydrate and Zn-Ni-acetate complexes. We found that the coordinated organic moieties are crucial for forming heterojunctions and their superior catalytic activity. We analyzed two antagonistic reactions to evaluate the performance of the catalysts and found that while the heterostructure of Ni-NiO-ZnO and their cooperative synergy were crucial for managing the effectiveness and selectivity of the catalyst for dehydrogenation of aryl alkanes/alkenes, they failed to enhance the hydrogenation of nitro arenes. The hydrogenation reaction was influenced by the shape, surface properties, and interaction of the hydroxide and oxide of both zinc and nickel, particularly accessible Ni(0). The catalysts showed functional group tolerance, multiple reusabilities, broad substrate applicability, and good activity for both reactions.

Synthesis of 5-(arylmethylideneamino)-4-(1H-benzo[d]imidazol-1-yl)pyrimidine hybrids: synthetic sequence and the molecular and supramolecular structures of two intermediates and three final products.

A concise and versatile synthesis of 5-(arylmethylideneamino)-4-(1H-benzo[d]imidazol-1-yl)pyrimidines has been developed, starting from 4-(1H-benzo[d]imidazol-1-yl)pyrimidines, and we report here the synthesis and spectroscopic and structural characterization of three such products, along with those of two intermediates in the reaction pathway. The intermediates 4-[2-(4-chlorophenyl)-1H-benzo[d]imidazol-1-yl]-6-methoxypyrimidine-2,5-diamine, (II), and 4-[2-(4-bromophenyl)-1H-benzo[d]imidazol-1-yl]-6-methoxypyrimidine-2,5-diamine, (III), crystallize as the isostructural monohydrates C18H15ClN5O·H2O and C18H15BrN5O·H2O, respectively, in which the components are linked into complex sheets by O-H...N and N-H...O hydrogen bonds. In the product (E)-4-methoxy-5-[(4-nitrobenzylidene)amino]-6-[2-(4-nitrophenyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, which crystallizes as a 1:1 solvate with dimethyl sulfoxide, C25H18N8O5·C2H6OS, (IV), inversion-related pairs of the pyrimidine component are linked by N-H...N hydrogen bonds to form cyclic centrosymmetric R22(8) dimers to which pairs of solvent molecules are linked by N-H...O hydrogen bonds. (E)-4-Methoxy-5-[(4-methylbenzylidene)amino]-6-[2-(4-methylphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, C27H24N6O, (V), crystallizes with Z'= 2 and the molecules are linked into a three-dimensional framework structure by a combination of N-H...N, C-H...N and C-H...π(arene) hydrogen bonds. The analogous product (E)-4-methoxy-5-[(4-chlorobenzylidene)amino]-6-[2-(4-methylphenyl)-1H-benzo[d]imidazol-1-yl]pyrimidin-2-amine, C26H21ClN6O, (VI), crystallizes from dimethyl sulfoxide in two forms: one, denoted (VIa), is isostructural with (V), and the other, denoted (VIb), crystallizes with Z'= 1, but as an unknown solvate in which the pyrimidine molecules are linked by N-H...N hydrogen bonds to form a ribbon containing two types of centrosymmetric ring.