Chemistry, An Asian Journal

The pincer complexes [NiIIBr(CNC)]Br (4), [CrIIIBr3(CNC)] (5a) and [CrIIIBr2.3Cl0.7(CNC)] (5b), where CNC = 3,3'-(pyridine-2,6-diyl)bis(1-mesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene), were obtained from the novel ligand CNC, generated in situ from the precursor (CHNCH)Br2 and [NiIIBr2(PPh3)2] or from [CrII{N(SiMe3)2}2(THF)2] and (CHNCH)Br2 by aminolysis, respectively. The tetrahedrally distorted square planar (τ4 ≅ 0.30) geometry and the singlet ground state of Ni in 4 were attributed to steric constraints of the CNC backbone...

Due to the serious ecological problems caused by the high CO2 content in the atmosphere, reducing atmospheric CO2 has attracted widespread attention from academia and governments. Among the many ways to mitigate CO2 concentration, the capture and comprehensive utilization of CO2 through chemical methods have obvious advantages, whose key is to develop suitable adsorbents and catalysts. Frustrated Lewis pairs (FLPs) are known to bind CO2 through the interaction between unquenched Lewis acid sites/Lewis base sites with the O/C of CO2, simultaneously achieving CO2 capture and activation, which render FLP better potential for CO2 utilization...

Pollution from harmful heavy metal ions such as Pb(II) and Cu(II) is causing serious environmental and health problems. In this study, Sodium and nitrogen co-doped porous carbon material (Na/NABc) was successfully prepared from seaweed, sodium hydroxide, and dicyandiamide. The experimental results showed that Na/NABc is an excellent adsorbent for the effective removal of Pb(II) and Cu(II) from water bodies. Specifically, 99.8% of Pb(II) and 64.6% Cu(II) (100 mg/L) were removed within 12 h using 10 mg Na/NABc(10%) at 25 °C...

Endoplasmic reticulum (ER) is one of the most important sub-cellular organelles which controls myriads of biological functions including protein biosynthesis with proper functional folded form, protein misfolding, protein transport into Golgi body for secretion, Ca2+ homeostasis and so on. Subsequently, dysregulation in ER function leads to ER stress followed by disease pathology like cancer. Hence, targeting ER in the cancer cells emerged as one of the futuristic strategies for cancer treatment. However, the major challenge is to selectively and specifically target ER in the sub-cellular milieu in the cancer tissues, due to the lack of ER targeting chemical moieties to recognize the ER markers...

Reactivity and regioselectivity of SNAr-type fluorine substitution with azide in polyfluoronitrobenzenes was studied both theoretically and experimentally. The obtained polyazidonitrobenzene derivatives were extensively characterized by NMR, IR, HPLC, X-ray, and DFT methods. It was found that the substitution with the azide nucleophile occurs first at the para- and the ortho-positions to the NO2-group and that transazidation reactions also occur here. Thermal decomposition of prepared azidonitrobenzenes was studied both in controlled (kinetic decay) and uncontrolled (explosion) modes...

A mild protocol for hydroacylation of enones through photosensitization of acyl silanes with thioxanthone under blue light (455 nm) irradiation is reported. A Brønsted acid is used as a co-catalyst in the reaction. The versatility of the method is demonstrated through inter- and intramolecular hydroacylation reaction. The hydroacylation product is applied for synthesizing an anti-HCV agent. Mechanistic insights are also provided through control experiments.

N,N,P-Pincer nickel complexes effectively catalyze reaction of alcohols with benzylphosphine oxides to form alkenes in good yields. The protocol suits for a wide scope of substrates and generates only E-configurated alkenes. The method also shows good compatibility of functional groups. Methoxy, methylthio, trifluoromethyl, ketal, fluoro, chloro, bromo, thienyl, and furyl groups are tolerated. The mechanism studies support that the reaction proceeds through catalytic dehydrogenation of alcohols to aldehydes or ketones followed by condensation with benzyldiphenylphosphine oxides in the presence of KOtBu...

Herein, we report an in-situ mild and metal-free protocol for thiomethylation of heteroarenes in high yields. The thiomethylation of various chloropurines, nucleosides, and chloroheteroarenes has been accomplished offering easy access to agrochemicals and synthetic molecules useful for drug discovery.

Plastics are versatile materials, offering lightweight, durable, and affordable solutions across various industries. However, their non-degradable nature poses challenges by end of their life. This study presented an innovative carbonyl extraction method to utilize waste poly(bisphenol A carbonate) (PC) as reaction precursor to synthesis of activated furan as precursor for photoswitchable Stenhouse adducts. This innovative chemical strategy not only generated N,N'-functionalized barbiturates but also provided an eco-friendly and cost-effective alternative to traditional synthesis methods...

By a reaction of trimethylphosphine with an open-[60]fullerene, corresponding dimers could be generated via two-fold deoxygenation processes even though the formation of β-oxo-phosphorous ylide is inevitable, a part of which is hydrolyzed to yield an α-methylene carbonyl derivative. Nevertheless, Wittig reaction and aldol condensation did not proceed well, indicating the presence of an unknown dimerization pathway. In the ylide formation, 1-phosphonium-3-carbabetaine was previously proposed as a key intermediate...

(C-X) bonds (X= C, N, O) are the main backbone for making different skeleton in the organic synthetic transformations. Among all the sustainable techniques, electro-organic synthesis for    C-X bond formation is the advanced tool as it offers a greener and more cost-effective approach to chemical reactions by utilizing electrons as reagents.  In this review, we want to explore the recent advancements in electrochemical C-O bond formation. The electrochemically driven C-O bond formation represents an emerging and exciting area of research...

Hydrogen has been regarded as a promising alternative to traditional fossil fuels, presenting itself as a viable and environmentally friendly energy choice. The design and fabrication of highly efficient hydrogen storage materials is crucial to the wide utilization of hydrogen-based technologies. Magnesium-based nanocrystalline materials have received significant interest in the field of hydrogen storage due to their remarkable hydrogen storage capabilities and release efficiency. This review emphasizes on the most useful techniques including vapor deposition, sol-gel synthesis, electrochemical deposition, magnetron sputtering, and template-assisted approaches used for the fabrication of Magnesium-based nanocrystalline hydrogen storage materials (Mg-NHSMs), stressing their advantages, limitations, and recent advancements...

Controlled insertion into a single P-P bond of white phosphorus (P4) was achieved by employing a diaryl stabilized stannylene, Ar*2Sn (Ar* = 2,6-bis(benzhydryl)-4-iPr-phenyl). Conversions of the stannylene with P4 gave a non-pyrophoric, air-stable storage compound, which releases P4 quantitively upon irradiation with light (354 or 455 nm). Alternatively, the phosphorus cage is detached by reacting the storage compound with PhChChPh (Ch = Se, Te). Despite the recent advances in the directed conversion of P4 using main group element compounds, Ar*2Sn constitutes only the second structurally characterized example of a stannylene capable of performing controlled, reversible addition and release of white phosphorus...

Photodynamic therapy (PDT) as an emerging therapeutic method has drawn many attentions in the treatment field for cancer. Photosensitizer, which can convert photon energy into cytotoxic species under light irradiation, is the core component in PDT. The design of photosensitizers still faces problems of light absorption, targeting, penetration and oxygen dependence. With the rapid progress of material science, various photosensitizers have been developed to produce cytotoxic species for treatment of tumor with high selectivity, safety, and noninvasiveness...

Diarylethenes (DAE), a class of best performing photoswitchable compounds, where the key features of stability, photoisomerization wavelengths, quantum yield and variability in the photoisomers significantly depend on their derivatization. The last decade has witnessed a surge in the engagement of DAEs to different areas of chemical and biological impacts like catalysis in synthetic organic chemistry, biological markers for in vivo imaging of live cells, chemosensing within cells to photo-dynamic therapy by controlled generation of singlet oxygen...

Based on the prior observation of the trifluoroacetate hypoiodite, CF3C(O)OI, demonstrating the largest σ-hole of a neutral halogen bond donor, a series of mono- and bis-carbonyl hypoiodites utilising trifluoromethyl or fluorine substituents at various positions of a parent benzoyl skeleton have been synthesised. The carbonyl hypoiodite complexes were prepared via cation exchange of the silver(I) cations with iodine(I) from the respective silver(I) carboxylates and dicarboxylates as the synthetic precursors...

Regio- and chemo-selective functionalization of electron deficient azaarenes often required their transformations to corresponding N-oxides and subsequent removal of oxygen after functionalization to get back the desired substituted azaarenes. An efficient metal-free visible-light photo-redox catalytic deoxygenation of N-oxides of azaheterocyclic compounds has been developed using acridinium based organo-photocatalyst in blue LED light. High efficiency and mildness of this methodology has been demonstrated through higher deoxygenation yield of wide variety of azaheterocyclic N-oxides with reactive functional groups...

Palladium-catalyzed thioarylation of indoles by diaryl disulfides in the presence of phenyliododiacetate is reported. The directing potential of weakly coordinating aldehyde group present at 3-position of indole was exploited for regioselective C2-H thioarylation over the possible C4-H functionalization. Mechanistic studies reveal that the process involves initial generation of thioaryl radical followed by sequential C-H activation, thiolate transfer, and reductive elimination.

A domino one-pot synthesis of 2-(trifluoromethyl)benzothiazole via copper-mediated three-component cascade reaction starting from the easily accessible starting materials such as o-iodoanilines, methyl trifluoropyruvate, and elemental sulfur is reported. The present strategy displayed a comprehensive substrate scope and good functional group tolerance and enabled access to a variety of substituted 2-(trifluoromethyl)benzothiazoles. A 2-(trifluoromethyl)benzoselenazole has also been synthesized utilizing this reaction methodology...

Carbon capture, utilization, and storage (CCUS) are among the key technologies to achieve large-scale carbon emission reduction globally. Deep eutectic solvents (DESs) are considered as designable solvents, which has attracted intensive attention for CO2 capture. Here, a series of binary DESs are synthesized through one-step mixing with the starting materials of protic ionic liquid (PIL) and amine. The eutectic behavior was investigated by measuring the melting point of PILs and amine. The saturated vapor of these DESs and industrial MDEA solution were measured and compared...