4485-08-9Relevant articles and documents
Ene reaction of singlet oxygen, triazolinedione, and nitrosoarene with chiral deuterium-labeled allylic alcohols: The interdependence of diastereoselectivity and regioselectivity discloses mechanistic insights into the hydroxy-group directivity
Adam, Waldemar,Bottke, Nils,Krebs, Oliver,Lykakis, Ioannis,Orfanopoulos, Michael,Stratakis, Manolis
, p. 14403 - 14409 (2002)
The ene reaction of singlet oxygen (1O2), triazolinedione (TAD), and nitrosoarene, specifically 4-nitronitrosobenzene (ArNO), with the tetrasubstituted 1,3-allylically strained, chiral allylic alcohol 3,4- dimethylpent-3-en-2-ol (2)
Transketolase Catalyzed Synthesis of N-Aryl Hydroxamic Acids
Fúster Fernández, Inés,Hecquet, Laurence,Fessner, Wolf-Dieter
, p. 612 - 621 (2021/12/08)
Hydroxamic acids are metal-chelating compounds that show important biological activity including anti-tumor effects. We have recently engineered the transketolase from Geobacillus stearothermopilus (TKgst) to convert benzaldehyde as a non-natur
Active ester functionalized azobenzenes as versatile building blocks
Schultzke, Sven,Staubitz, Anne,Walther, Melanie
supporting information, (2021/07/12)
Azobenzenes are important molecular switches that can still be difficult to functionalize selectively. A high yielding Pd-catalyzed cross-coupling method under mild conditions for the introduction of NHS esters to azobenzenes and diazocines has been established. Yields were consistently high with very few exceptions. The NHS functionalized azobenzenes react with primary amines quantitatively. These amines are ubiquitous in biological systems and in material science.
Phenylimino Indolinone: A Green-Light-Responsive T-Type Photoswitch Exhibiting Negative Photochromism
Buma, Wybren Jan,Crespi, Stefano,Di Donato, Mariangela,Doria, Sandra,Feringa, Ben L.,Hilbers, Michiel F.,Kiss, Ferdinand L.,Simeth, Nadja A.,Stindt, Charlotte N.,Szymański, Wiktor,Toyoda, Ryojun,Wesseling, Sammo
supporting information, p. 25290 - 25295 (2021/10/25)
Imines are photoaddressable motifs useful in the development of new generations of molecular switches, but their operation with low-energy photons and control over isomer stability remain challenging. Based on a computational design, we developed phenylimino indolinone (PIO), a green-light-addressable T-type photoswitch showing negative photochromism. The isomerization behavior of this photoactuator of the iminothioindoxyl (ITI) class was studied using time-resolved spectroscopies on time scales from femtoseconds to the steady state and by quantum-chemical analyses. The understanding of the isomerization properties and substituent effects governing these photoswitches opens new avenues for the development of novel T-type visible-light-addressable photoactuators based on C=N bonds.
Photochromic Evaluation of 3(5)-Arylazo-1 H-pyrazoles
Rustler, Karin,Nitschke, Philipp,Zahnbrecher, Sophie,Zach, Julia,Crespi, Stefano,K?nig, Burkhard
, p. 4079 - 4088 (2020/04/09)
The desire to photocontrol molecular properties ranging from materials to pharmacology using light as an external trigger with high spatiotemporal resolution led to the development of a broad range of photochromic scaffolds. Among them, azobenzenes are synthetically well accessible and show excellent fatigue resistance. Their photochromic properties vary with the substitution pattern and for different heteroarenes. However, the photochromism of 3(5)-substituted-1H-pryazoles has not yet been investigated, although this compound class offers interesting possibilities of metal ion coordination and hydrogen bond formation via its NH moiety. Herein, we present the results of an experimental and computational investigation of arylazo-3(5)-arylazo-1H-pyrazoles. To elucidate their properties, solvent and substitution effects on their light absorption, thermal half-lives, photostationary states, fatigue, and quantum yields were determined.
Reversible Photocontrolled Nanopore Assembly
Mutter, Natalie L.,Volari?, Jana,Szymanski, Wiktor,Feringa, Ben L.,Maglia, Giovanni
supporting information, p. 14356 - 14363 (2019/10/11)
Self-assembly is a fundamental feature of biological systems, and control of such processes offers fascinating opportunities to regulate function. Fragaceatoxin C (FraC) is a toxin that upon binding to the surface of sphingomyelin-rich cells undergoes a s
Light-Switchable Antagonists for the Histamine H1 Receptor at the Isolated Guinea Pig Ileum
Rustler, Karin,Pockes, Steffen,K?nig, Burkhard
, p. 636 - 644 (2019/02/14)
The histamine H1 G protein-coupled receptor (GPCR) plays an important role in allergy and inflammation. Existing drugs that address the H1 receptor differ in their chemical structure, pharmacology, and side effects. Light-controllable spatial and temporal activity regulation of photochromic H1 ligands may contribute to a better mechanistic understanding and the development of improved correlations between ligand structure and pharmacologic effects. We report photochromic H1 receptor ligands, which were investigated in an organ-pharmacological assay. Initially, five photochromic azobenzene derivatives of reported dual H1–H4 receptor antagonists were designed, synthesized, photochemically characterized, and organ-pharmacologically tested on the isolated guinea pig ileum. Among them, one compound [trans-19: (Z)-1-(4-chlorophenyl)-1-(4-methylpiperazin-1-yl)-N-(4-((E)-phenyldiazenyl)phenyl)methanimine] retained the antagonistic activity of its non-photochromic lead, and trans–cis isomerization by irradiation induced a fourfold difference in the pharmacological response. Further structural optimization resulted in two bathochromically shifted derivatives of 19 [NO2-substituted 35 {(Z)-1-(4-chlorophenyl)-1-(4-methylpiperazin-1-yl)-N-(4-((E)-(4-nitrophenyl)diazenyl)phenyl)methanimine} and SO3?-substituted 41 {4-((E)-(4-(((Z)-(4-chlorophenyl)(4-methylpiperazin-1-yl)methylene)amino)phenyl)diazenyl)benzenesulfonate}], which do not require the use of UV light for photoisomerization and which also have improved solubility and show reduced tissue impairment. The trans isomers of both compounds showed a remarkable increase in antagonistic activity relative to their lead trans-19; furthermore, a 46-fold difference in activity on the isolated guinea pig ileum was observed between trans- and cis-35.
Synthesis of Functionalized Azobiphenyl- and Azoterphenyl- Ditopic Linkers: Modular Building Blocks for Photoresponsive Smart Materials
Grosjean, Sylvain,Hodapp, Patrick,Hassan, Zahid,W?ll, Christof,Nieger, Martin,Br?se, Stefan
, p. 743 - 759 (2019/07/03)
Modular synthesis of structurally diverse functionalized azobiphenyls and azoterphenyls for the realization of optically switchable materials has been described. The corresponding synthesis of azobiphenyls and azoterphenyls by stepwise Mills/Suzuki-Miyaura cross-coupling reaction, proceeds with high yields and provides facile access to a library of functionalized building blocks. The synthetic methods described herein allow combining several distinct functional groups within a single unit, each intended for a specific task, such as 1) the ?N=N? azobenzene core as a photoswitchable moiety, 2) aryls and heteroaryls, functionalized with carboxylic acids or pyridine at its peripheries, as coordinating moieties and 3) varying substitution, size and length of the backbone for adaptability to specific applications. These specifically designed azobiphenyls and azoterphenyls provide modular bricks, potentially useful for the assembly of a variety of polymers, molecular containers and coordination networks, offering a high degree of molecular functionality. Once integrated into materials, the azobenzene system, as a side group on the organic linker backbone, can be exploited for remotely controlling the structural, mechanical or physical properties, thus being applicable for a broad variety of ‘smart’ applications.
Tungstate-supported silica-coated magnetite nanoparticles: a novel magnetically recoverable nanocatalyst for green synthesis of nitroso arenes
Jadidi Nejad, Masoume,Yazdani, Elahe,Kazemi Miraki, Maryam,Heydari, Akbar
, p. 1575 - 1583 (2019/09/09)
Tungstate ion was heterogenized on the silica-coated magnetite nanoparticles and applied for the selective oxidation of anilines to nitroso arenes—with hydrogen peroxide/urea as oxidant in dimethyl carbonate as solvent—in moderate–good yields (40–96%). The catalyst was characterized using different techniques including Fourier-transform infrared spectroscopy, X-ray powder diffraction, vibrating sample magnetometry, scanning electron microscopy, energy dispersive X-ray and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The catalyst was easily recovered using an external magnet and reused for six times.
Novel Phenyldiazenyl Fibrate Analogues as PPAR α/γ/δ Pan-Agonists for the Amelioration of Metabolic Syndrome
Giampietro, Letizia,Laghezza, Antonio,Cerchia, Carmen,Florio, Rosalba,Recinella, Lucia,Capone, Fabio,Ammazzalorso, Alessandra,Bruno, Isabella,De Filippis, Barbara,Fantacuzzi, Marialuigia,Ferrante, Claudio,MacCallini, Cristina,Tortorella, Paolo,Verginelli, Fabio,Brunetti, Luigi,Cama, Alessandro,Amoroso, Rosa,Loiodice, Fulvio,Lavecchia, Antonio
supporting information, p. 545 - 551 (2019/03/19)
The development of PPARα/γ dual or PPARα/γ/δ pan-agonists could represent an efficacious approach for a simultaneous pharmacological intervention on carbohydrate and lipid metabolism. Two series of new phenyldiazenyl fibrate derivatives of GL479, a previously reported PPARα/γ dual agonist, were synthesized and tested. Compound 12a was identified as a PPAR pan-agonist with moderate and balanced activity on the three PPAR isoforms (α, γ, δ). Moreover, docking experiments showed that 12a adopts a different binding mode in PPARγ compared to PPARα or PPARδ, providing a structural basis for further structure-guided design of PPAR pan-agonists. The beneficial effects of 12a were evaluated both in vitro, on the expression of PPAR target key metabolic genes, and ex vivo in two rat tissue inflammatory models. The obtained results allow considering this compound as an interesting lead for the development of a new class of PPAR pan-agonists endowed with an activation profile exploitable for therapy of metabolic syndrome.
