Aryl Research Articles

Palladium‐katalysierte decarbonylierende Iodierung von Carbonsäuren, ermöglicht durch Ligand‐unterstützten Halogenaustausch

AbstractWir berichten über eine effiziente und breit anwendbare Palladium‐katalysierte Iodierung günstiger und leicht verfügbarer Aryl‐ und Vinylcarbonsäuren durch In‐situ‐Aktivierung zum Säurechlorid und Bildung eines Phosphoniumsalzes. Die Verwendung von 1‐Iodbutan als Iodidquelle in Kombination mit einer Base und einem Desoxychlorierungsreagenz eröffnet den Zugang zu einer Vielzahl von Aryl‐ und Vinyliodiden unter Pd/Xantphos‐Katalyse, einschließlich komplexer arzneimittelähnlicher Strukturen. Stöchiometrische Experimente und kinetische Analysen legen einen einzigartigen Mechanismus nahe, welcher die reduktive C‐P‐Eliminierung zur Bildung des Xantphos‐Phosphoniumchlorids beinhaltet, welches anschließend einen ungewöhnlichen Halogenaustausch durch nukleophile Substitution initiiert.

Synthesis of structurally diversified BINOLs and NOBINs via palladium-catalyzed C-H arylation with diazoquinones

Synthesis of structurally diversified BINOLs and NOBINs via palladium-catalyzed C-H arylation with diazoquinones

Aryl C-H iodination: are there actual flavin-dependent iodinases in nature?

Aryl C-H iodination: are there actual flavin-dependent iodinases in nature?

Rhodium‐katalysierte dealkenylierende Arylierung von Alkenen mit Arylboronverbindungen

AbstractDie C‐C‐Bindungsbildungsreaktion stellt eine fundamentale und wichtige Transformation in der Synthesechemie dar, und die Erforschung neuer Arten von C‐C‐Bindungsbildungsreaktionen gilt als reizvoll, aber auch als Herausforderung. Hier wird das erste Beispiel einer Rhodium‐katalysierten dealkenylierenden Arylierung von Alkenen mit Arylboronverbindungen vorgestellt, die einen unkonventionellen Zugang zu Bi(hetero)arylen mit exzellenter Chemoselektivität ermöglicht. Bei dieser Methode können C(Aryl)‐C(Alkenyl)‐ und C(Alkenyl)‐C(Alkenyl)‐Bindungen in verschiedenen Alkenen und 1,3‐Dienen über eine Hydrometallierung und einen anschließenden β‐Kohlenstoff‐Eliminierungsweg für Suzuki‐Miyaura‐Reaktionen gespalten werden. Darüber hinaus wurde eine Reihe neuartiger organischer fluoreszierender Moleküle mit exzellenten photophysikalischen Eigenschaften effizient hergestellt.

Highly Efficient Nanocrytalline Zeolite Catalyst for the Hydroxyalkylation of Anisole with Benzaldehyde

The heterogeneous solid acid catalyzed hydroxyalkylation of arenes with benzaldehyde yields triarylmethane (TRAM) compounds which have gained significant attention due to their notable application in dyes, pharmaceuticals and the synthesis of various functional materials. In the present study the activity of nanocrystalline Beta and ZSM-5 zeolites was studied in the liquid phase hydroxyalkylation of anisole with benzaldehyde. The catalysts were characterized by Dynamic Light Scattering measurements, an X-ray diffraction study and scanning electron microscope and transmission electron microscope analyses. The reaction parameters, such as-catalyst loading, mole ratio, reaction temperature, and catalyst reusability were optimized. The efficiency of zeolite catalysts having different pore sizes was tested under the optimum reaction conditions. The results showed that the larger pore of nanocrystalline Beta exhibited the highest activity, which was due to the increased pore size of the crystal for the easy adsorption of reactants and the desorption of bulky products. It is important to highlight that the nanocrystalline Beta catalysts showed higher efficiency compared to other reported results in the literature, with the advantage of high activity, selectivity, separation of the catalyst and excellent reusability. Therefore, these catalysts can be used instead of conventional homogeneous catalysts such as AlCl3, ZnCl2 and H2SO4 for an eco-friendly selective production of tri aryl methane compounds.

Innentitelbild: New Synthetic Approaches to N‐Aryl and π‐Expanded Diketopyrrolopyrroles as New Building Blocks for Organic Optoelectronic Materials (Angew. Chem. 19/2021)

Diketopyrrolopyrrole (DPPs) sind wichtige Verbindungen als Bausteine für organische optoelektronische Materialien. In ihrem Forschungsartikel auf S. 10795 berichten Deqing Zhang et al. über eine neue Synthesemethode für N-Aryl-DPPs und π-expandierte DPPs. Diese neuen DPP-Moleküle zeigen vielversprechende Emissions- und Halbleitereigenschaften, was ihre Nützlichkeit für die Entwicklung hochleistungsfähiger organischer optoelektronischer Materialien demonstriert.

A Choosy Arylene Macrocycle that Likes to Fly Solo

A Choosy Arylene Macrocycle that Likes to Fly Solo

Metal-free synthesis of biarenes via photoextrusion in di(tri)aryl phosphates.

A metal-free route for the synthesis of biarenes has been developed. The approach is based on the photoextrusion of a phosphate moiety occurring upon irradiation of biaryl- and triaryl phosphates. The reaction involves an exciplex as the intermediate and it is especially suitable for the preparation of electron-rich biarenes.

Palladium-Catalyzed C(sp3)–H Arylation of Peptides Assisted by Unmodified Asparagine

Palladium-Catalyzed C(sp3)–H Arylation of Peptides Assisted by Unmodified Asparagine

Aspergillus nidulans: A Potential Resource of the Production of the Native and Heterologous Enzymes for Industrial Applications.

Aspergillus nidulans is a filamentous fungus that is a potential resource for industrial enzymes. It is a versatile fungal cell factory that can synthesize various industrial enzymes such as cellulases, β-glucosidases, hemicellulases, laccases, lipases, proteases, β-galactosidases, tannases, keratinase, cutinases, and aryl alcohol oxidase. A. nidulans has shown the potential to utilize low-cost substrates such as wheat bran, rice straw, sugarcane bagasse, rice bran, coir pith, black gram residue, and chicken feathers to produce enzymes cost-effectively. A. nidulans has also been known as a model organism for the production of heterologous enzymes. Several studies reported genetically engineered strains of A. nidulans for the production of different enzymes. Native as well as heterologous enzymes of A. nidulans have been employed for various industrial processes.

Synthesis of novel N‐aryl‐N‐(1H‐tetrazol‐5‐yl)benzenesulfonamides in water

N‐Aryl‐N‐(1H‐tetrazol‐5‐yl)benzenesulfonamides were synthesized via an eco‐friendly protocol using ZnBr2‐catalyzed [2 + 3] cycloaddition reaction of N‐cyano‐N‐arylbenzenesulfonamides and sodium azide under reflux conditions in water. The products were obtained in excellent yields via an easy work‐up procedure.

D-carvone attenuates biochemical and molecular expression via oncogenic signaling in aryl hydrocarbon-induced hamster mucosal carcinogenesis

Background: Chemo prevention through nutritional constituents has appeared as an innovative methodology to control the oral cancer incidence. The main target of this research exists to explore the chemopreventive effect of D-carvone by way of biochemical and molecular prototype during 7,12-dimethylbenz[a]anthracene (DMBA)-stimulated hamsters mucosal carcinogenesis. Materials and Methods: Topical application of 0.5% DMBA in liquid paraffin, thrice a week, for 10 weeks well developed oral squamous cell carcinoma in hamsters cheek pouch (HCP). All the same 100% tumor formation was perceived in hamsters induced with DMBA alone, but intragastric administration of D-carvone, at a dose of 10 mg/kg bw, to DMBA-treated hamster totally prevented the formation of oral tumor. Results: D-carvone significantly lessens lipid peroxidation (LPO) by-products and enhanced the status of enzymatic, non-enzymatic antioxidants, and varied the status of Phase I and II xenobiotic enzymes, favoring the secretion of cancer metabolites through downregulation of proliferating cell nuclear antigen and p53 expression during oral tumor hamsters. Conclusion: The nearby study suggests that D-carvone relies on its anti-LPO, antioxidant, xenobiotic metabolic enzymes as well as anti-cell proliferation and induced apoptosis during DMBA-induced hamster oral mucosal carcinogenesis.

Levels of aryl hydrocarbon receptor nuclear translocator in lung tissue of children with congenital heart disease pulmonary hypertension and its effect on proliferation and migration of pulmonary artery smooth muscle cells

Objective To observe the levels of aryl hydrocarbon receptor nuclear translocator (ARNT) in lung tissue of children with congenital heart disease (CHD) pulmonary artery hypertension (PAH) and its effect on proliferation and migration of human pulmonary artery smooth muscle cells (HPASMCs), and to investigate the action mechanism of ARNT in the pathogenesis of CHD-PAH. Methods Sixty patients with CHD ventricular septal defect-associated PAH were selected as CHD-PAH group and 60 children with CHD ventricular septal defect without PAH were selected as CHD group (CHD group) in our hospital. There were no significant difference in age and gender between the two groups. HPASMCs were divided into normoxia group and hypoxia group, which were induced by normoxia and hypoxia respectively. HPASMCs were divided into blank control group (BC group), negative control group (NC group) and siR-ARNT group. The cells in the siR-ARNT group were transfected with ARNT-shRNA lentivirus, and those in the NC group were transfected with negative control lentivirus. The cells in the BC group were not transfected. The expression levels of ARNT protein and mRNA in lung tissue and cells were detected by Western blotting and reverse transcription-polymerase chain reaction (RT-PCR). The cell proliferation ability was determined by the cell counting kit-8 (CCK-8) method. Transwell and scratch assays were used to measure cell migration ability. SPSS 20.0 software was used for analysis. The test methods were t test and analysis of variance. Results The expression levels of ARNT protein and mRNA in lung tissue of CHD-PAH group (0.53±0.06 and 2.36±0.17) were significantly higher than those in CHD group (0.09±0.02, 1.00±0.12, t=53.889 and 50.626, P 0.05). Conclusion The ARNT levels in lung tissue of children with CHD-PAH are elevated. ARNT may participate in the development of CHD-PAH by affecting the proliferation and migration of HPASMCs. Key words: Congenital heart disease; Pulmonary hypertension; Aryl hydrocarbon receptor nuclear translocation protein; Pulmonary artery smooth muscle cells; Proliferation; Migration

Nickel-catalyzed and Li-mediated regiospecific C–H arylation of benzothiophenes

A sustainable nickel-catalyzed direct C–H arylation of benzothiophenes, benzofuran and selenophene is reported for the first time.

Synthesis and anti-tuberculosis studies of 10-phenyl sulfonyl-2-alkyl/aryl- 4, 10 dihydrobenzo [4, 5] imidazo [1, 2-a] pyrimidin-4-one derivatives

Synthesis and anti-tuberculosis studies of 10-phenyl sulfonyl-2-alkyl/aryl- 4, 10 dihydrobenzo [4, 5] imidazo [1, 2-a] pyrimidin-4-one derivatives

Pd/Chiral Phosphoric Acid-Catalyzed Enantioselective β-C(sp3)—H Arylation of Thiamides

Pd/Chiral Phosphoric Acid-Catalyzed Enantioselective <i>β</i>-C(sp³)—H Arylation of Thiamides

Two Novel Compounds with Tri-aryl Structures as Effective Anti-Breast Cancer Candidates In-vivo.

Prognosis of metastatic breast cancer is very poor which urges the necessity to develop novel potential drug candidates. We assessed two compounds with tri-aryl structures (A and B) for their potency to reduce primary breast tumor growth and lung metastasis in 4T1 mice model. MTT assay, 4T1 mammary mouse model, and immunohistochemistry experiments were used in this study. In-vitro results exhibited an anti–proliferative effect for compounds A and B towards MDA-MB-231 cancer cells. Our in-vivo results displayed that administered compounds A and B could suppress the size of the primary tumor and the number of lung metastatic foci in 4T1 BALB/c mice model. Histopathological analysis revealed that treatment of both compounds resulted in necrosis. Our findings provide new evidence that compound B may be promising for slowing the growth of tumor along with metastatic foci via COX-2 independent pathway.

Synthesis of Stable σ-Adducts by Arylation of Quinazoline

Synthesis of Stable σ-Adducts by Arylation of Quinazoline

Synthesis of Activated Amides and Directed C(sp3)–H Arylation

Synthesis of Activated Amides and Directed C(sp3)–H Arylation

Correction to “Gold-Catalyzed C–H Functionalization with Aryl Germanes”

Correction to “Gold-Catalyzed C–H Functionalization with Aryl Germanes”