Asian Journal of Organic Chemistry最新文献

A cascade alkylation/cyclization reaction of ortho-isocyanodiaryl amines with 1,3-dicarbonyl compounds in the presence of Mn(OAc)₃·2H₂O has been developed. This reaction offers an efficient protocol to alkylated dibenzodiazepines, and features simple and mild conditions, wide substrate scope, and good functional group tolerance. All of those examined products exhibited obvious cytotoxic activities against Hela, HepG-2, SGC-7901, and HL-60 cells at 20 µM. Compounds 3f, 3i, and 3r show better activity than 5-FU on SGC-7901 cells.

A selectfluor-mediated metal-free approach has been developed for the synthesis of methylene-bound benzotriazolation, triazolation, and pyrazolation of 3-acetylindoles at 90°C. The reaction is kinetically controlled and uses DMSO as one carbon source. Further, α-methylenation of 3-acetylindoles was observed when benzotriazole, triazole, and pyrazole were absent in the reaction at a higher temperature (120°C). The reaction uses DMSO as one-carbon synthon and is thermodynamically controlled. The base is needed for α-methylenation of 3-acetylindoles. The current method expands the scope of metal-free organic reactions and offers new opportunities for developing a library of bioactive indoles for pharmaceutical science.

Aryl benzene sulfonyl hydrazide derivatives containing electron-donor and electron-acceptor groups were successfully synthesized and reported via a one-pot manner, which showed remarkable optical properties. The changes in fluorescence properties of compound 5a in the presence of various cations were evaluated. Compound 5a can act as a fluorescence sensor for susceptible and selective detection of As³⁺ and Ru³⁺ in DMSO. DFT calculation was done to elucidate the mechanisms. Selectively respond to detecting As³⁺ and Ru³⁺ with enhanced and quenched fluorescence, respectively. The fluorescence of Job's plot supported the fluorescence of 5a, As³⁺, and Ru³⁺, as well as the sensing mechanism of the 1:1 binding system. The binding constants for the 5a + As³⁺ and 5a + Ru³⁺ were found to be 4.83 × 10⁻⁵ M⁻¹ and 1.91 × 10⁻⁵ M⁻¹, with LOD attained 1.91 × 10⁻⁷ M⁻¹ for As³⁺, and 2.01 × 10⁻⁷ M⁻¹ for Ru³⁺, respectively.

This mini review describes recent achievements in the production and chemical transformations of muconic acid (hexa-2,4-dienedioic acid, HO₂CCH═CHCH═CHCO₂H). Muconic acid may be obtained from renewable lignocellulosic materials, and it is considered as a bio-based platform molecule. This acid has a great practical value due to its hydrogenation into adipic acid, which is used for nylon production. Muconic acid and its derivatives take part in many important and useful synthetic transformations such as Diels-Alder reactions, isomerization, lactonization, polymerization, polycondensation, and others. However, up to the moment, muconic acid is not yet widely used in the fine organic synthesis. This review is focused on preparation, reactions, and on some novel applications of muconic acid and its derivatives in organic synthesis. The aim of this review is to attract attention to muconic acid, which has a high potential to be a valuable precursor for preparation of novel compounds and materials.

The discovery of novel molecular scaffolds broadens chemical space and supports innovative therapeutics. We identified the underexplored scaffold N-((3-hydroxycyclobutyl)(piperidin-4-yl)methyl)amide from the ChemBridge database using the similarity ensemble approach (SEA). Seven commercial analogs displayed modest cytotoxicity against prostate (PC-3, LNCaP) and pancreatic (PANC-1) cancer cells but significantly inhibited LPS-induced ROS and nitrite production in RAW 264.7 macrophages, suggesting anti-inflammatory potential. To expand this scaffold, we developed a modular synthesis. A Ni-catalyzed reductive coupling of a tosyl-protected iodopiperidine with 3-(benzyloxy)cyclobutane-1-carboxylic acid successfully provided a key ketone intermediate. Reductive amination and acylation yielded amide derivatives, demonstrating synthetic feasibility. Sodium naphthalenide enabled concurrent O-benzyl and N-tosyl deprotection, streamlining the sequence to six steps from simple starting materials. This modular route permits late-stage incorporation of diverse acyl fragments for analog diversification. Overall, N-((3-hydroxycyclobutyl)(piperidin-4-yl)methyl)amide is a synthetically accessible scaffold with promising anti-inflammatory activity, offering a foundation for further optimization and therapeutic development.

An additive-free and metal-free three-component radical relay reaction has been achieved to obtain diverse sulfonylated polycyclic indolines with moderate to excellent yields. This innovative protocol offers several significant advantages: (1) it eliminates the need for transition metal catalysts, (2) operates under mild reaction conditions without requiring high temperatures, and (3) demonstrates exceptional diastereoselectivity (dr > 20:1). Comprehensive mechanistic studies have revealed that the transformation proceeds through an intramolecular 1,5-hydrogen atom transfer (1,5-HAT) process.

A practical and efficient potassium trimethylsilanolate/nitrile system for constructing all-carbon quaternary centers has been developed. This transition-metal free protocol utilizes readily available chlorides and 1,3-dicarbonyl compounds, enabling the selective formation of two C─C bonds in a single operation. The reaction features broad substrate scope, good functional group tolerance, large scale synthesis, and further structural modification, providing a mild approach to access quaternary centers in moderate to excellent yields.

In this paper, we have developed an efficient and simple method for obtaining difluoromethylated benzothiophene derivatives under electrochemical conditions. The method utilizes 2-alkynylthioanisoles, which contain active alkynes as substrates, affordable sodium difluoromethanesulfinate (HCF₂SO₂Na) as the fluorinating reagent. By the anodic oxidation to excite difluoromethyl radicals under electrochemical conditions and triggering difunctionalization reactions through the addition of alkynes via free radicals to form target products. It features excellent functional group compatibility and affords a variety of benzothiophene derivatives in good yields.