scholarly journals Direct electrochemical generation of organic carbonates by dehydrogenative coupling

2018 ◽  
Vol 14 ◽  
pp. 1578-1582 ◽  
Author(s):  
Tile Gieshoff ◽  
Vinh Trieu ◽  
Jan Heijl ◽  
Siegfried R Waldvogel
Keyword(s):  
Reaction Pathway ◽  
Reaction Conditions ◽  
Electrochemical Generation ◽  
Organic Carbonates ◽  
Dehydrogenative Coupling ◽  
Reactive Chemicals ◽  
New Strategy ◽  
Methyl Carbonate

Organic carbonates are an important source for polycarbonate synthesis. However, their synthesis generally requires phosgene, sophisticated catalysts, harsh reaction conditions, or other highly reactive chemicals. We present the first direct electrochemical generation of mesityl methyl carbonate by C–H activation. Although this reaction pathway is still challenging concerning scope and efficiency, it outlines a new strategy for carbonate generation.

Ketones from Nickel-Catalyzed Decarboxylative, Non-Symmetric Cross-Electrophile Coupling of Carboxylic Acid Esters

2019 ◽  
Author(s):  
Jiang Wang ◽  
Brian P. Cary ◽  
Peyton Beyer ◽  
Samuel H. Gellman ◽  
Daniel Weix
Keyword(s):  
Carboxylic Acid ◽  
Solid Support ◽  
Reaction Conditions ◽  
Decarboxylative Coupling ◽  
New Strategy ◽  
The Cross ◽  
Acyl Donors ◽  
Acid Esters

A new strategy for the synthesis of ketones is presented based upon the decarboxylative coupling of N-hydroxyphthalimide (NHP) esters with S-2-pyridyl thioesters. The reactions are selective for the cross-coupled product because NHP esters act as radical donors and the thioesters act as acyl donors. The reaction conditions are general and mild, with over 40 examples presented, including larger fragments and the 20-mer peptide Exendin(9-39) on solid support.

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

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.

scholarly journals Self-Assembled Bimetallic Aluminum-Salen Catalyst for the Cyclic Carbonates Synthesis

Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 4097
Author(s):  
Wooyong Seong ◽  
Hyungwoo Hahm ◽  
Seyong Kim ◽  
Jongwoo Park ◽  
Khalil A. Abboud ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Self Assembly ◽  
Reaction Pathway ◽  
Kinetic Studies ◽  
Cyclic Carbonate ◽  
Reaction Conditions ◽  
Formation Reaction ◽  
X Ray ◽  
Carbonate Formation ◽  
Salen Aluminum

Bimetallic bis-urea functionalized salen-aluminum catalysts have been developed for cyclic carbonate synthesis from epoxides and CO2. The urea moiety provides a bimetallic scaffold through hydrogen bonding, which expedites the cyclic carbonate formation reaction under mild reaction conditions. The turnover frequency (TOF) of the bis-urea salen Al catalyst is three times higher than that of a μ-oxo-bridged catalyst, and 13 times higher than that of a monomeric salen aluminum catalyst. The bimetallic reaction pathway is suggested based on urea additive studies and kinetic studies. Additionally, the X-ray crystal structure of a bis-urea salen Ni complex supports the self-assembly of the bis-urea salen metal complex through hydrogen bonding.

scholarly journals Reaction Mechanism for Methane-to-Methanol in Cu-SSZ-13: First-Principles Study of the Z2[Cu2O] and Z2[Cu2OH] Motifs

Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 17
Author(s):  
Unni Engedahl ◽  
Adam A. Arvidsson ◽  
Henrik Grönbeck ◽  
Anders Hellman
Keyword(s):  
Liquid Fuel ◽  
Density Functional ◽  
Reaction Pathway ◽  
Direct Conversion ◽  
Reaction Conditions ◽  
Oxidation Of Methane ◽  
Small Pore ◽  
Desorption Step ◽  
Solution Gas ◽  
Stable Motif

As transportation continues to increase world-wide, there is a need for more efficient utilization of fossil fuel. One possibility is direct conversion of the solution gas bi-product CH4 into an energy-rich, easily usable liquid fuel such as CH3OH. However, new catalytic materials to facilitate the methane-to-methanol reaction are needed. Using density functional calculations, the partial oxidation of methane is investigated over the small-pore copper-exchanged zeolite SSZ-13. The reaction pathway is identified and the energy landscape elucidated over the proposed motifs Z2[Cu2O] and Z2[Cu2OH]. It is shown that the Z2[Cu2O] motif has an exergonic reaction path, provided water is added as a solvent for the desorption step. However, a micro-kinetic model shows that neither Z2[Cu2O] nor Z2[Cu2OH] has any notable activity under the reaction conditions. These findings highlight the importance of the detailed structure of the active site and that the most stable motif is not necessarily the most active.

scholarly journals Prebiotic Route to Thymine from Formamide—A Combined Experimental–Theoretical Study

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2248
Author(s):  
Lukáš Petera ◽  
Klaudia Mrazikova ◽  
Lukas Nejdl ◽  
Kristyna Zemankova ◽  
Marketa Vaculovicova ◽  
...  
Keyword(s):  
Formic Acid ◽  
Quantum Chemical ◽  
Prebiotic Chemistry ◽  
Theoretical Study ◽  
Reaction Pathway ◽  
Hydrolysis Product ◽  
Current Paper ◽  
Reaction Conditions ◽  
Chemical Modeling ◽  
Chemistry Research

Synthesis of RNA nucleobases from formamide is one of the recurring topics of prebiotic chemistry research. Earlier reports suggest that thymine, the substitute for uracil in DNA, may also be synthesized from formamide in the presence of catalysts enabling conversion of formamide to formaldehyde. In the current paper, we show that to a lesser extent conversion of uracil to thymine may occur even in the absence of catalysts. This is enabled by the presence of formic acid in the reaction mixture that forms as the hydrolysis product of formamide. Under the reaction conditions of our study, the disproportionation of formic acid may produce formaldehyde that hydroxymethylates uracil in the first step of the conversion process. The experiments are supplemented by quantum chemical modeling of the reaction pathway, supporting the plausibility of the mechanism suggested by Saladino and coworkers.

scholarly journals Nitrosonium ion catalysis: aerobic, metal-free cross-dehydrogenative carbon–heteroatom bond formation

2018 ◽  
Vol 54 (92) ◽  
pp. 13022-13025 ◽  
Author(s):  
Luis Bering ◽  
Laura D’Ottavio ◽  
Giedre Sirvinskaite ◽  
Andrey P. Antonchick
Keyword(s):  
Bond Formation ◽  
Environmentally Benign ◽  
Reaction Conditions ◽  
Metal Free ◽  
Dehydrogenative Coupling ◽  
Nitrosonium Ion

Catalytic cross-dehydrogenative coupling of heteroarenes with thiophenols and phenothiazines has been developed under mild and environmentally benign reaction conditions.

scholarly journals Unexpected Intrinsic Lability of Thiol-Functionalized Carboxylate Imidazolium Ionic Liquids

Molecules ◽  
2019 ◽  
Vol 24 (19) ◽  
pp. 3571
Author(s):  
Andrea Mezzetta ◽  
Lorenzo Poderelli ◽  
Felicia D’Andrea ◽  
Christian Silvio Pomelli ◽  
Cinzia Chiappe ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Ionic Liquids ◽  
Side Reaction ◽  
Switching Systems ◽  
Reaction Conditions ◽  
Imidazolium Ionic Liquids ◽  
Methyl Carbonate ◽  
Imidazolium Ring ◽  
Redox Switching ◽  
Insight Into

New thiol-functionalized carboxylate ionic liquids (ILs), varying both for the cation and for the anion structures, have been prepared as new potential redox switching systems by reacting either 3-mercapto propionic acid (3-MPA) or N-acetyl-cysteine (NAC) with commercially available methyl carbonate ILs. Different ratios of thiol/disulfide ILs were obtained depending both on the acid employed in the neutralization reaction and on the reaction conditions used. Surprisingly, the imidazolium ILs displayed limited thermal stability which resulted in the formation of an imidazole 2-thione and a new sulfide ionic liquid. Conversely, the formation of the imidazole 2-thione was not observed when phosphonium disulfide ILs were heated, thus confirming the involvement of the imidazolium ring in an unexpected side reaction. An insight into the mechanism of the decomposition has been provided by means of DFT calculations.

scholarly journals Manganese-mediated reductive functionalization of activated aliphatic acids and primary amines

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Zhan Li ◽  
Ke-Feng Wang ◽  
Xin Zhao ◽  
Huihui Ti ◽  
Xu-Ge Liu ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Late Stage ◽  
Materials Science ◽  
Reaction Pathway ◽  
Chemical Conversion ◽  
Primary Amines ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Aliphatic Acids ◽  
Redox Active

Abstract Alkyl carboxylic acids as well as primary amines are ubiquitous in all facets of biological science, pharmaceutical science, chemical science and materials science. By chemical conversion to redox-active esters (RAE) and Katritzky’s N-alkylpyridinium salts, respectively, alkyl carboxylic acids and primary amines serve as ideal starting materials to forge new connections. In this work, a Mn-mediated reductive decarboxylative/deaminative functionalization of activated aliphatic acids and primary amines is disclosed. A series of C-X (X = S, Se, Te, H, P) and C-C bonds are efficiently constructed under simple and mild reaction conditions. The protocol is applicable to the late-stage modification of some structurally complex natural products or drugs. Preliminary mechanistic studies suggest the involvement of radicals in the reaction pathway.

Polymerization and oxidation of phenols in supercritical water

2019 ◽  
Vol 80 (4) ◽  
pp. 620-633 ◽  
Author(s):  
Huiwen Zhang ◽  
Xiaoman Zhang ◽  
Lei Ding ◽  
Miao Gong ◽  
Ying Su ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Phenolic Compounds ◽  
Supercritical Water ◽  
Water Oxidation ◽  
Reaction Pathway ◽  
Radical Reaction ◽  
Dominant Factor ◽  
Supercritical Water Oxidation ◽  
Free Radical Reaction ◽  
Reaction Conditions

Abstract The treatment of toxic and difficult-to-degrade phenolic compounds has become a key issue in the coking, pharmaceutical, and chemical industries. Considering the polymerization and oxidation of phenolic compounds in supercritical water partial oxidation/supercritical water oxidation (SCWPO/SCWO), the present study reviewed the removal efficiency and reaction pathway of phenolic compounds and phenolic waste/wastewater under different reaction conditions. Temperature is the dominant factor affecting the SCWO reaction. When the oxidizing ability is insufficient, the organics polymerize to form phenolic compounds. The gradual increase of oxidant equivalent causes the intermediate product to gradually oxidize to CO2 and H2O completely. Finally, the free radical reaction mechanism is considered to be a typical SCWO reaction mechanism.

scholarly journals Full N,N-Methylation of 4,4′-Methylenedianiline with Dimethyl Carbonate: A Feasible Access to 4,4′-Methylene bis(N,N-Dimethylaniline)

2018 ◽  
Vol 2018 ◽  
pp. 1-10
Author(s):  
Zegang Qiu ◽  
Kunjie Wang ◽  
Zhiqin Li ◽  
Tao Li ◽  
Jinhao Bai ◽  
...  
Keyword(s):  
Zinc Acetate ◽  
Dimethyl Carbonate ◽  
Reaction Pathway ◽  
Major Product ◽  
High Yield ◽  
Synthetic Route ◽  
Reaction Conditions ◽  
High Yields ◽  
By Products

The full N,N-methylation of 4,4′-methylenedianiline (MDA) with dimethyl carbonate (DMC) was investigated. The yield of the major product 4,4′-methylene bis(N,N-dimethylaniline) (MBDMA) reached as high as 97% over NaY catalyst at 190°C for 6 h. The catalyst could be used for two more times with acceptable MBDMA yields higher than 90%. The main by-products were identified as three N-methylated derivatives. Surprisingly, the formation of the N-methoxycarbonylation product was extremely restrained, which could be produced in high yields of 98% on zinc acetate catalyst. Furthermore, the reaction pathway to the major product MBDMA was proposed. Finally, a feasible synthetic route of 4,4′-methylene bis(N,N-dimethylaniline) (MBDMA) was established, featuring a high yield, mild reaction conditions, and simple operations.

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