112776-83-7Relevant articles and documents
Unprecedented strong lewis bases - Synthesis and methyl cation affinities of dimethylamino-substituted terpyridines
Hommes, Paul,Fischer, Christina,Lindner, Christoph,Zipse, Hendrik,Reissig, Hans-Ulrich
, p. 7647 - 7651 (2014)
A versatile method for the synthesis of functionalized 2,2′:6′, 2″-terpyridines by assembly of the terminal pyridine rings is presented. The cyclization precursors - bis-β-ketoenamides - are prepared from 4-substituted 2,6-pyridinedicarboxylic acids and a
Design and synthesis of polyoxazole-based macrocycles tethered with a phosphonate group
Qi, Fuling,Gao, Lianxun,Han, Fushe
, p. 585 - 591 (2014)
We present the design and synthesis of polyoxazole-based macrocycles containing a phosphonate group. A reliable route was established that allows for convenient and versatile incorporation of various phosphonate functionalities such as phosphonate ester, acid, and salt at the macrocyclic ring periphery. Such unprecedented macrocyclic compounds are anticipated to be appealing candidates as telomerase inhibitors. Copyright
Photo-responsive cyclodextrin/anthracene/Eu3+ supramolecular assembly for a tunable photochromic multicolor cell label and fluorescent ink
Zhou, Weilei,Chen, Yong,Yu, Qilin,Li, Peiyu,Chen, Xuman,Liu, Yu
, p. 3346 - 3352 (2019)
A photo-responsive supramolecular assembly was successfully constructed through the stoichiometric 2?:?1 non-covalent association of two 4-(anthracen-2-yl)pyridine-2,6-dicarboxylic acid (1) units in one γ-cyclodextrin (γ-CD) cavity, followed by the subsequent coordination polymerization of the γ-CD·12 (12 = two 1) inclusion complex with Eu(iii). Interestingly, owing to the photodimerization behavior of anthracene units and the excellent luminescence properties of Eu(iii), the Eu3+?γ-CD·12 system showed multicolor fluorescence emission from cyan to red by irradiation for 0-16 minutes. Moreover, white light emission with CIE coordinates (0.32 and 0.36) was achieved at 4 min. Importantly, white light-containing multicolor emission could be obtained in water, solid films and living cells. Especially, the Eu3+?γ-CD·12 system could tag living cells with marvelous white fluorescence and display no obvious cytotoxicity. Thus, this supramolecular assembly offers a new pathway in the fields of tunable photochromic fluorescent ink and cell labelling.
Synthesis of a 'propeller-like' oligoheteroaryl with alternating pyridine and oxazole motifs
Georgiades, Savvas N.,Rizeq, Natalia
, p. 489 - 493 (2015)
The molecular architecture of oligomeric pyridyl-oxazole compounds is key to determining their mode of interaction with G-quadruplex DNA structures, which is a family of prominent anticancer biomolecular targets. We report herein an efficient synthetic route that begins with chelidamic acid and affords, in just seven steps, an unusual 'propeller-like' pyridyl-oxazole architecture with alternating pyridine and oxazole rings, that has not been yet validated as a G-quadruplex binder. The synthesis employs Van Leusen chemistry for the construction of oxazole rings from aldehydes, and two Pd(II)/Cu(I)-mediated cross-coupling reactions involving C-H activation of oxazoles for the formation of C-C bonds between bromopyridine intermediates and oxazole fragments. This modular synthesis was designed to be amenable to the construction of analogues.
Efficient Syntheses of New Super Lewis Basic Tris(dialkylamino)-Substituted Terpyridines and Comparison of Their Methyl Cation Affinities
Kleoff, Merlin,Suhr, Simon,Sarkar, Biprajit,Zimmer, Reinhold,Reissig, Hans-Ulrich,Marin-Luna, Marta,Zipse, Hendrik
, p. 7526 - 7533 (2019)
Syntheses of very electron-rich dialkylamino-substituted 2,2':6',2''-terpyridines (TPYs) were adapted to moderate scale preparation without tedious purification of intermediates. The key 4'-bromo-6,6''-dimethyl-2,2':6',2''-terpyridine-4,4''-diyl bisnonaflate is now available in gram quantities. Its nucleophilic aromatic substitution with dimethylamine provided mixtures of 4'-bromo-substituted 4,4''-bis(dimethylamino)-TPY and the tris(dimethylamino)-TPY. The bromo compound was used in a Buchwald–Hartwig amination to provide the tris(dimethylamino)-TPY in excellent yield. The 4'-bromo substituent was reductively removed to furnish the bis(dimethylamino)-TPY. The same sequence of reactions with pyrrolidine as nucleophile leads to the hitherto unknown pyrrolidino-TPYs. Calculations at the MP2(FC)/6–31+G(2d,p)//B98/6-31G(d) level predict very high methyl cation affinities for compounds of this type, with the 4,4',4''-tri(pyrrolidin-1-yl)-TPY being the most Lewis basic TPY synthesized to date. The efficiently prepared electron-rich TPYs should be excellent ligands for many applications.
Thiol-ene reaction: A versatile tool in site-specific labelling of proteins with chemically inert tags for paramagnetic NMR
Li, Qing-Feng,Yang, Yin,Maleckis, Ansis,Otting, Gottfried,Su, Xun-Cheng
, p. 2704 - 2706 (2012)
Site-specific tagging of proteins with paramagnetic lanthanides generates valuable long-range structure restraints for structural biology by NMR spectroscopy. We show that the thiol-ene addition reaction offers a powerful tool for tagging proteins in a chemically stable manner with very small lanthanide tags. The Royal Society of Chemistry 2012.
Effects of a halogenated G-quadruplex ligand from the pyridine dicarboxamide series on the terminal sequence of XpYp telomere in HT1080 cells
Sidibe, Assitan,Hamon, Florian,Largy, Eric,Gomez, Dennis,Teulade-Fichou, Marie-Paule,Trentesaux, Chantal,Riou, Jean-Francois
, p. 2559 - 2568 (2012)
Non-canonical four-stranded structures called G-quadruplexes can form among telomere repeats during its replication. Small molecule ligands able to interact and to stabilize G-quadruplexes were shown to disrupt the binding of essential telomeric components, such as POT1 and to trigger a telomeric dysfunction associated with a delayed growth arrest in tumor cells. We describe here the chemical synthesis and the G-quadruplex binding properties of three halogenated analogs of the 360A ligand that belongs to the 2,6 pyridine dicarboxamide series. 360A is now commonly used as a benchmark both for biophysical and cellular assays as this compound was shown to display a potent affinity and selectivity for telomeric G-quadruplex DNA over duplex DNA and to induce delayed growth inhibition in HT1080 tumor cell line. Two biophysical assays indicate that, in most cases, the presence of the halogen atom seems to slightly improve the interaction with the telomeric quadruplex. For stability reasons, the bromo derivative (360A-Br) was selected for the cellular assays. Since POT1 participates to the fine tuning of the C-strand end resection during telomere replication, we investigated the effect of 360A-Br to alter the terminal nucleotide composition of XpYp telomere in HT1080 cells using C-STELA. HT1080 cells treated for up to 24 days with 360A-Br presented some minor but significant variations of C-strand terminal nucleotide composition, also observed with a partial siRNA depletion of POT1. The relevance of these minor modifications of the telomeric C-strand resection induced by 360A-Br in HT1080 cells are discussed.
Influence of a Metal Substrate on Small-Molecule Activation Mediated by a Surface-Adsorbed Complex
Schlimm, Alexander,Stucke, Nadja,Fl?ser, Benedikt M.,Rusch, Talina,Krahmer, Jan,N?ther, Christian,Strunskus, Thomas,Magnussen, Olaf M.,Tuczek, Felix
, p. 10732 - 10744 (2018)
Activating small molecules with transition metal complexes adsorbed on metal surfaces is a novel approach combining aspects of homogeneous and heterogeneous catalysis. In order to study the influence of an Au(111) substrate on the activation of the small-molecule ligand carbon monoxide, a molybdenum tricarbonyl complex containing a PN3P pincer ligand was synthesized and investigated in the bulk, in solution, and adsorbed on an Au(111) surface. By means of a platform approach, a perpendicular orientation of the molybdenum complex was achieved and confirmed by IRRAS and NEXAFS. By using vibrational spectroscopy (IR, Raman, IRRAS) coupled to DFT calculations, the influence of the metal substrate on the activation of the CO ligands bound to the molybdenum complex was determined. The electron-withdrawing behavior of gold causes an overall shift of the CO stretching vibrations to higher frequencies, which is partly compensated by dynamic charge transfer from the substrate to the molybdenum center, which increases its (dynamic) polarizability.
