Dehydrogenative Coupling of Alkanes and Benzene Enhanced by Slurry-Phase Interparticle Hydrogen Transfer

Although it is recognized that niacin (pyridine-3-carboxylic acid), incorporated as the amide in nicotinamide adenine dinucleotide (NAD) or in nicotinamide adenine dinucleotide phosphate (NADP), is a cofactor in hydrogen transfer in numerous enzyme reactions in all organisms studied, virtually no information is available on the effect of this vitamin on a cell at the submicroscopic level. Since mitochondria act as sites for many hydrogen transfer processes, the possible response of mitochondria to niacin treatment is, therefore, of critical interest.Onion bulbs were placed on vials filled with double distilled water in the dark at 25°C. After two days the bulbs and newly developed root system were transferred to vials containing 0.1% niacin. Root tips were collected at ¼, ½, 1, 2, 4, and 8 hr. intervals after treatment. The tissues were fixed in glutaraldehyde-OsO4 as well as in 2% KMnO4 according to standard procedures. In both cases, the tissues were dehydrated in an acetone series and embedded in Reynolds' lead citrate for 3-10 minutes.

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Cobalt/Lewis Acid Catalysis for Hydrocarbofunctionalization of Alkynes via Cooperative C–H Activation

10.26434/chemrxiv.11760519.v1 ◽

2020 ◽

Author(s):

Chang-Sheng Wang ◽

Sabrina Monaco ◽

Anh Ngoc Thai ◽

Md. Shafiqur Rahman ◽

Chen Wang ◽

...

Keyword(s):

Catalytic System ◽

Lewis Acid ◽

Hydrogen Transfer ◽

Acid Catalysis ◽

Rate Limiting Step ◽

Site Selectivity ◽

Set Up ◽

Site Selective ◽

First Time ◽

Rate Limiting

A catalytic system comprised of a cobalt-diphosphine complex and a Lewis acid (LA) such as AlMe3 has been found to promote hydrocarbofunctionalization reactions of alkynes with Lewis basic and electron-deficient substrates such as formamides, pyridones, pyridines, and azole derivatives through site-selective C-H activation. Compared with known Ni/LA catalytic system for analogous transformations, the present catalytic system not only feature convenient set up using inexpensive and bench-stable precatalyst and ligand such as Co(acac)3 and 1,3-bis(diphenylphosphino)propane (dppp), but also display distinct site-selectivity toward C-H activation of pyridone and pyridine derivatives. In particular, a completely C4-selective alkenylation of pyridine has been achieved for the first time. Mechanistic stidies including DFT calculations on the Co/Al-catalyzed addition of formamide to alkyne have suggested that the reaction involves cleavage of the carbamoyl C-H bond as the rate-limiting step, which proceeds through a ligand-to-ligand hydrogen transfer (LLHT) mechanism leading to an alkyl(carbamoyl)cobalt intermediate.

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Thermally-Induced Dehydrogenative Coupling of Organosilanes and H-Terminated Silicon Quantum Dots onto Germanane Surfaces

10.26434/chemrxiv.11794404 ◽

2020 ◽

Author(s):

Haoyang Yu ◽

Alyxandra Thiessen ◽

Md Asjad Hossain ◽

Marc Julian Kloberg ◽

Bernhard Rieger ◽

...

Keyword(s):

2D Materials ◽

Future Generation ◽

Optical Devices ◽

Surface Reactivity ◽

Organic Monolayers ◽

Present Contribution ◽

Thermally Induced ◽

Dehydrogenative Coupling ◽

Silicon Quantum Dot ◽

Covalently Bonded

<div><div><div><p>Covalently bonded organic monolayers play important roles in defining the solution processability, ambient stability, and electronic properties of two-dimensional (2D) materials such as Ge nanosheets (GeNSs); they also hold promise of providing avenues for the fabrication of future generation electronic and optical devices. Functionalization of GeNS normally involves surface moieties linked through covalent Ge−C bonds. In the present contribution we extend the scope of surface linkages to include Si−Ge bonding and present the first demonstration of heteronuclear dehydrocoupling of organosilanes to hydride-terminated GeNSs obtained from the deintercalation and exfoliation of CaGe2. We further exploit this new surface reactivity and demonstrated the preparation of directly bonded silicon quantum dot-Ge nanosheet hybrids.</p></div></div></div>

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Nanometer Scale Spectroscopic Visualization of Catalytic Sites During a Hydrogenation Reaction on a Pd/Au Bimetallic Catalyst

10.26434/chemrxiv.12346823.v3 ◽

2020 ◽

Author(s):

hao yin ◽

Liqing Zheng ◽

Wei Fang ◽

Yin-Hung Lai ◽

Nikolaus Porenta ◽

...

Keyword(s):

Catalytic Hydrogenation ◽

Density Functional ◽

Hydrogen Transfer ◽

Bimetallic Catalyst ◽

Local Environment ◽

Hydrogenation Reaction ◽

Boundary Density ◽

Catalytic Sites ◽

Powerful Analytical Tool ◽

Tip Enhanced Raman Spectroscopy

<p>Understanding the mechanism of catalytic hydrogenation at the local environment requires chemical and topographic information involving catalytic sites, active hydrogen species and their spatial distribution. Here, tip-enhanced Raman spectroscopy (TERS) was employed to study the catalytic hydrogenation of chloro-nitrobenzenethiol on a well-defined Pd(sub-monolayer)/Au(111) bimetallic catalyst (<i>p</i><sub>H2</sub>=1.5 bar, 298 K), where the surface topography and chemical fingerprint information were simultaneously mapped with nanoscale resolution (≈10 nm). TERS imaging of the surface after catalytic hydrogenation confirms that the reaction occurs beyond the location of Pd sites. The results demonstrate that hydrogen spillover accelerates hydrogenation at the Au sites within 20 nm from the bimetallic Pd/Au boundary. Density functional theory was used to elucidate the thermodynamics of interfacial hydrogen transfer. We demonstrate that TERS as a powerful analytical tool provides a unique approach to spatially investigate the local structure-reactivity relationship in catalysis.</p>

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Nanometer Scale Spectroscopic Visualization of Catalytic Sites During a Hydrogenation Reaction on a Pd/Au Bimetallic Catalyst

10.26434/chemrxiv.12346823.v1 ◽

2020 ◽

Author(s):

Hao Yin ◽

Liqing Zheng ◽

Wei Fang ◽

Yin-Hung Lai ◽

Nikolaus Porenta ◽

...

Keyword(s):

Catalytic Hydrogenation ◽

Density Functional ◽

Hydrogen Transfer ◽

Bimetallic Catalyst ◽

Local Environment ◽

Hydrogenation Reaction ◽

Boundary Density ◽

Catalytic Sites ◽

Powerful Analytical Tool ◽

Tip Enhanced Raman Spectroscopy

<p>Understanding the mechanism of catalytic hydrogenation at the local environment requires chemical and topographic information involving catalytic sites, active hydrogen species and their spatial distribution. Here, tip-enhanced Raman spectroscopy (TERS) was employed to study the catalytic hydrogenation of chloro-nitrobenzenethiol on a well-defined Pd(sub-monolayer)/Au(111) bimetallic catalyst (<i>p</i><sub>H2</sub>=1.5 bar, 298 K), where the surface topography and chemical fingerprint information were simultaneously mapped with nanoscale resolution (≈10 nm). TERS imaging of the surface after catalytic hydrogenation confirms that the reaction occurs beyond the location of Pd sites. The results demonstrate that hydrogen spillover accelerates hydrogenation at the Au sites within 20 nm from the bimetallic Pd/Au boundary. Density functional theory was used to elucidate the thermodynamics of interfacial hydrogen transfer. We demonstrate that TERS as a powerful analytical tool provides a unique approach to spatially investigate the local structure-reactivity relationship in catalysis.</p>

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A Facile One-pot Synthesis of Substituted Quinolines via Cascade Friedlander Reaction from Isoxazoles with Ammonium Formate-Pd/C and Ketones

Letters in Organic Chemistry ◽

10.2174/1570178616666190618091617 ◽

2020 ◽

Vol 17 (3) ◽

pp. 211-215

Author(s):

Da Chen ◽

Xuan Wang ◽

Runnan Wang ◽

Yao Zhan ◽

Xiaohan Peng ◽

...

Keyword(s):

Hydrogen Transfer ◽

Ammonium Formate ◽

Aromatic Ketone ◽

Reaction Conditions ◽

One Pot ◽

Diverse Range ◽

Strong Base ◽

Aromatic Ketones ◽

Substituted Quinolines ◽

New Strategy

The Friedlander reaction is the most commonly used method to synthesis substituted quinolines, the essential intermediates in the medicine industry. A facile one-pot approach for synthesizing substituted quinolines by the reaction of isoxazoles, ammonium formate-Pd/C, concentrated sulfuric acid, methanol and ketones using Friedlander reaction conditions is reported. Procedures for the synthesis of quinoline derivatives were optimized, and the yield was up to 90.4%. The yield of aromatic ketones bearing electron-withdrawing groups was better than the ones with electron-donating substituents. The structures of eight substituted quinolines were characterized by MS, IR, H-NMR and 13CNMR, which were in agreement with the expected structures. The mechanism for the conversion was proposed, which involved the Pd/C catalytic hydrogen transfer reduction of unsaturated five-membered ring of isoxazole to produce ortho-amino aromatic ketones. Then the nucleophilic addition of with carbonyl of the ketones generated Schiff base in situ, which underwent an intermolecular aldol reaction followed by the elimination of H2O to give production of substituted quinolines. This new strategy can be readily applied for the construction of quinolines utilizing a diverse range of ketones and avoids the post-reaction separation of the o-amino aromatic ketone compounds. The conventionally used o-amino aromatic ketone compounds in Friedlander reaction to prepare substituted quinoline are laborious to synthesize and are apt to self-polymerize. While oxazole adopted in this work can be prepared at ease by the condensation of benzoacetonitrile and nitrobenzene derivatives under the catalysis of a strong base. Moreover, the key features of this protocol are readily available starting materials, excellent functional group tolerance, mild reaction conditions, operational simplicity, and feasibility for scaling up.

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Transition-Metal-Free Synthetic Strategies for the Cross-Coupling Reactions in Water: A Green Approach

Current Green Chemistry ◽

10.2174/2213346107999201006193653 ◽

2020 ◽

Vol 07 ◽

Author(s):

Tanmay Chatterjee ◽

Nilanjana Mukherjee

Keyword(s):

Transition Metal ◽

Organic Solvents ◽

Aqueous Media ◽

Cross Coupling ◽

Transition Metal Catalysts ◽

Synthetic Methods ◽

Coupling Reactions ◽

Organic Transformations ◽

Green Approach ◽

Dehydrogenative Coupling

Abstract: A natural driving force is always working behind the synthetic organic chemists towards the development of ‘green’ synthetic methodologies for the synthesis of useful classes of organic molecules having potential applications. The majority of the essential classes of organic transformations, including C-C and C-X (X = heteroatom) bond-forming crosscoupling reactions, cross dehydrogenative-coupling (CDC) mostly rely on the requirement of transition-metal catalysts and hazardous organic solvents. Hence, the scope in developing green synthetic strategies by avoiding the use of transitionmetal catalysts and hazardous organic solvents for those important and useful classes of organic transformations is very high. Hence, several attempts are made so far. Water being the most abundant, cheap, and green solvent in the world; numerous synthetic methods have been developed in an aqueous medium. In this review, the development of transitionmetal- free green synthetic strategies for various important classes of organic transformations such as C-C and C-X bondforming cross-coupling, cross dehydrogenative-coupling, and oxidative-coupling in an aqueous media is discussed.

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Intermolecular hydrogen transfer in unsaturated hydrocarbons induced by dimeric titanocene

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19832924 ◽

1983 ◽

Vol 48 (10) ◽

pp. 2924-2936 ◽

Cited By ~ 5

Author(s):

Karel Mach ◽

Lidmila Petrusová ◽

Helena Antropiusová ◽

Vladimír Hanuš ◽

František Tureček ◽

...

Keyword(s):

Hydrogen Transfer ◽

Titanium Content ◽

Esr Spectra ◽

Stable Complex ◽

Catalytic Complex ◽

Substitution Reactions ◽

Unsaturated Hydrocarbons ◽

Linear Alkanes ◽

Saturated And Aromatic Hydrocarbons ◽

Intermolecular Hydrogen Transfer

μ-(η5 : η5-Fulvalene)-di-μ-hydrido-bis(η5-cyclopentadienyltitanium) and μ-(η5 : η5-fulvalene)-μ-chloro-μ-hydrido-bis(cyclopentadienyltitanium) form a thermally stable complex which catalyzes the intermolecular hydrogen transfer in unsaturated hydrocarbons, in addition to isomerizations and cyclizations. Cyclic hydrocarbons disproportionate under catalysis to saturated and aromatic hydrocarbons, while linear olefins yield predominantly linear alkanes and high molecular weight tar. The catalyst enables the hydrocarbon system to approach the thermodynamic equilibrium through a series of substitution reactions between alkyl- and allyltitanocene-like species and olefins and dienes. The catalytic complex was characterized by UV and ESR spectra. About one half of overall titanium content could be converted to mononuclear η3-allyltitanocene-like species, stable up to 400 °C. This exceptional thermal stability is ascribed to a firmly bound allyl containing ligand.

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Electrostatic effects on ionization equilibria: An MNDO study of proton and hydrogen transfer reactions of 4-fluorobutylamine

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19900001 ◽

1990 ◽

Vol 55 (1) ◽

pp. 1-9 ◽

Cited By ~ 1

Author(s):

Zdeněk Friedl ◽

Stanislav Böhm

Keyword(s):

Hydrogen Transfer ◽

Substituent Effects ◽

Radical Cations ◽

Transfer Reactions ◽

Protonated Forms ◽

Minor Part ◽

Bond Strengths ◽

Ionization Equilibria ◽

A Minor ◽

Gas Phase Basicities

The relative enthalpies of proton transfer δ ΔH0and homolytic bond strengths δDH0(B-H+) were calculated by the MNDO method for the sp and ap conformers of 4-flurobutylamine. The data obtained, along with the experimental gas phase basicities, are compared with the values predicted by the electrostatic theory. It is shown that the substituent polar effects FD on the basicities of amines are predominantly due to interactions in their protonated forms (X-B-H+) and/or radical-cations (X-B+.), those in the neutral species (X-B) playing a minor part. A contribution, which is considerably more significant in the sp conformer than in the ap conformer, arises probably also from substituent effects on the homolytic bond strength DH0(B-H+.

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Ruthenium-catalyzed synthesis of N-substituted lactams by acceptorless dehydrogenative coupling of diols with primary amines

Chemical Communications ◽

10.1039/c9cc06339k ◽

2019 ◽

Vol 55 (82) ◽

pp. 12384-12387 ◽

Cited By ~ 3

Author(s):

Yanling Zheng ◽

Xufeng Nie ◽

Yang Long ◽

Li Ji ◽

Haiyan Fu ◽

...

Keyword(s):

Phosphine Ligand ◽

Primary Amines ◽

Dehydrogenative Coupling ◽

One Step

The first synthesis of N-substituted lactams via an acceptorless dehydrogenative coupling of diols with primary amines in one step was enabled by combining Ru3(CO)12 with a hybrid N-heterocyclic carbene–phosphine–phosphine ligand as the catalyst.

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