Preparation and characterization of Cu (II) Schiff base complex functionalized boehmite nanoparticles and its application as an effective catalyst for oxidation of sulfides and thiols

The synthesis, characterization, and evaluation of a Schiff base Cu (II) complex functionalized boehmite nanoparticles (Cu-complex-boehmite) as a new catalyst for oxidation of sulfides and thiols in the presence of hydrogen peroxide with complete selectivity and high conversion under solvent-free and mild reaction conditions were reported. Characterization of the catalyst was performed with various physicochemical methods. This effective catalyst was evaluated in terms of activity and reusability. It indicated high catalytic activity, good recoverability and reusability, and supplied the corresponding products in high yields and short reaction times. In addition, it shows notable advantages such as simplicity of operation, heterogeneous nature, easy work up, and it could be used at least eight times with no significant loss of its activity.     

Monitoring the changes of 5-caffeoylquinic acid during its reaction with ABTS cation radicals by LC-MS

Abstract

Reactive oxygen species including free radicals are responsible for noxious changes in living organisms which can be associated with many diseases for e.g. cardiovascular, neurodegenerative, and inflammatory diseases or cancer. In the struggle against free radicals the organism is supported by antioxidants. As they are often provided by nature, they can be considered safe. 5-Caffeoylquinic acid is one of main chlorogenic acids found in vegetables and fruits. The main objective of the presented article was monitoring the changes of 5-caffeoylquinic acid during the reaction with colorful radicals. The experiments were conducted at different molar ratios of radicals to antioxidant using liquid chromatography–mass spectrometry. Irrespective of the applied molar ratios, the obtained results proved that the antioxidant takes part in the reaction for three days. Additionally, during the radical neutralization the formation of semiquinones and/or quinones, methoxy adduct of caffeoylquinic acid, and quinones adduct with methanol was observed.     

Chiral Ligands in Hypervalent Iodine Compounds: Synthesis and Structures of Binaphthyl-Based λ3-Iodanes

Several novel binaphthyl-based chiral hypervalent iodine(III) reagents have been prepared and structurally analysed. Various asymmetric oxidative reactions were applied to evaluate the reactivities and stereoselectivities of those reagents. Moderate to excellent yields were observed; however, very low stereoselectivities were obtained. NMR experiments indicated that these reagents are very easily hydrolysed in either chloroform or DMSO solvents leading to the limited stereoselectivities. It is concluded that the use of chiral ligands is an unsuccessful way to prepare efficient stereoselective iodine(III) reagents.     

Recent advances in electrochemical water technologies for the treatment of antibiotics: A short review

This short review presents a critical overview of the most recent works published in the literature related to the use of electrochemical advanced oxidation processes (EAOPs) for the treatment of antibiotics present in synthetic and real wastewaters. The first section focuses on novelties within the traditional EAOPs, including electrochemical oxidation and electrochemical Fenton-based processes. The second section is devoted to new electrochemical technologies, including heterogeneous electro-Fenton, electrochemically activated persulfate processes, and combined processes. Future perspectives about these processes are also presented to aid the continuous evolution of research in the area.     

Asymmetric electrosynthesis: Recent advances in catalytic transformations

Asymmetric synthesis is one of the most important and valuable research fields in modern organic chemistry. Since the use of electricity as a traceless oxidant or reductant under electrochemical conditions, highly reactive intermediates can selectively generate under mild reaction conditions through more environmentally benign conditions compared with the reactions using common chemical oxidants or reductants. Thus, the merging electrochemistry with asymmetric catalysis would provide a unique and powerful approach for the synthesis of optically active compounds under oxidative or reductive conditions. Selected recent (2018–2020) examples of enantioselective electro-organic synthesis using transition metal catalysts or organocatalysts are summarized in this short review. These examples are divided to oxidative and reductive transformations and described together with brief reaction mechanisms.     

Oxidation with a “Stopover” – Stable Zwitterions as Intermediates in the Oxidation of α-Tocopherol (Vitamin E) Model Compounds to their Corresponding ortho-Quinone Methides

As a prominent member of the vitamin E group, α-tocopherol is an important lipophilic antioxidant. It has a special oxidation chemistry that involves phenoxyl radicals, quinones and quinone methides. During the oxidation to the ortho-quinone methide, an intermediary zwitterion is formed. This aromatic intermediate turns into the quinone methide by simply rotating the initially oxidized, exocyclic methyl group into the molecule's plane. This initial zwitterionic intermediate and the quinone methide are not resonance structures but individual species, whose distinct electronic structures are separated by a mere 90° bond rotation. In this work, we hindered this crucial rotation, by substituting the affected methyl group with alkyl or phenyl groups. The alkyl groups slowed down the conversion to the quinone methide by 18-times, while the phenyl substituents, which additionally stabilize the zwitterion electronically, completely halted the conversion to the quinone methide at −78 °C, allowing for the first time the direct observation of a tocopherol-derived zwitterion. Employing a ¹³C-labeled model, the individual steps of the oxidation sequence could be observed directly by NMR, and the activation energy for the rotation could be estimated to be approximately 2.8 kcal/mol. Reaction rates were solvent dependent, with polar solvents exerting a stabilizing effect on the zwitterion. The observed effects confirmed the central relevance of the rotation step in the change from the aromatic to the quinoid state and allowed a more detailed examination of the oxidation behavior of tocopherol. The concept that a simple bond rotation can be used to switch between an aromatic and an anti-aromatic structure could find its use in molecular switches or molecular engines, driven by the specific absorption of external energy.     

Selective Photocatalytic Oxidation of Sulfides in Lanthanide Metal -Organic Frameworks Incorporating Ru(2,2′-bpy)3 photosensitizer

Three isostructural lanthanide metal-organic frameworks (Ln-MOFs) were synthesized with uncoordinated N^N site, and the Ru(N^N)₃ photosensitizer was introduced via coordination link. These functionalized frameworks showed excellent performance in the photocatalytic oxidation of sulfides with good conversion and high sulfoxide selectivity.     

Selective oxidation of benzylic,allylic and propargylic alcohols using dirhodium(II) tetraamidinate as catalyst and aqueous tert‐butyl hydroperoxide as oxidant

We show that the dirhodium(II) tetraamidinate complex Rh₂(Msip)₄ efficiently catalyzes the oxidation of activated secondary alcohols at only 0.1 mol% loading. In this approach, we oxidized various benzylic, allylic and propargylic alcohols to the corresponding carbonyl compounds under mild aqueous conditions using the inexpensive oxidant T‐HYDRO® (70 wt% aqueous tert‐butyl hydroperoxide). Copyright © 2015 John Wiley & Sons, Ltd.     

One‐Pot Synthesis of O‐Allylhydroxylamines through the Organocatalytic Oxidation of Tertiary Allylic Amines Followed by a [2,3]‐Meisenheimer Rearrangement

A cheap, green, and highly efficient one‐pot method for the synthesis of O‐protected allylic alcohols is described. By utilizing 2,2,2‐trifluoroacetophenone as the organocatalyst and H₂O₂ as the oxidant, a variety of allylic amine N‐oxides were synthesized, which upon heating are converted to the final products through a [2,3]‐Meisenheimer rearrangement.     

Palladium(II)‐Catalyzed Dehydroboration via Generation of Boron Enolates

The Pd^II‐catalyzed dehydroboration of boron enolates generated from ketones and 9‐iodo‐9‐borabicyclo[3.3.1]nonane was achieved, providing a synthetically versatile protocol from ketones to α,β‐unsaturated ketones. The Pd^II compound employed in this reaction worked catalytically in the presence of Cu(OAc)₂. The high trans‐selectivity of the olefinic moiety was observed. Aryl halide moieties (‐Br and ‐Cl) remained intact for this reaction in spite of the presence of a Pd species. An ester substrate could also be applied when a stoichiometric amount of Pd^II was used. The crossover reactions using boron and silyl enolates revealed that the oxidation reaction is much faster than the Saegusa‐Ito reaction.