- Synthesis and characterization of two different azarubrenes
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The synthesis, properties and solid state X-ray single crystal structures of two new rubrene-derivatives, viz diazarubrene (4,4′-(6,12-diphenyltetracene-5,11-diyl)dipyridine) and tetraazarubrene (5,6,11,12-tetra(pyridin-4-yl)tetracene), are reported. Both the azarubrenes are more oxidatively stable than rubrene itself and show very similar optical properties but differ in their crystal packing from that of rubrene.
- Xie, Gaozhan,Hahn, Sebastian,Rominger, Frank,Freudenberg, Jan,Bunz, Uwe H. F.
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Read Online
- Synergetic effect of host-guest chemistry and spin crossover in 3D hofmann-like metal-organic frameworks [Fe(bpac)M(CN)4] (M=Pt, Pd, Ni)
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The synthesis and characterization of a series of three-dimensional (3D) Hofmann-like clathrate porous metal-organic framework (MOF) materials [Fe(bpac)M(CN)4] (M=Pt, Pd, and Ni; bpac=bis(4-pyridyl)acetylene) that exhibit spin-crossover behavior is reported. The rigid bpac ligand is longer than the previously used azopyridine and pyrazine and has been selected with the aim to improve both the spin-crossover properties and the porosity of the corresponding porous coordination polymers (PCPs). The 3D network is composed of successive {Fe[M(CN)4]}n planar layers bridged by the bis-monodentate bpac ligand linked in the apical positions of the iron center. The large void between the layers, which represents 41.7% of the unit cell, can accommodate solvent molecules or free bpac ligand. Different synthetic strategies were used to obtain a range of spin-crossover behaviors with hysteresis loops around room temperature; the samples were characterized by magnetic susceptibility, calorimetric, Moessbauer, and Raman measurements. The complete physical study reveals a clear relationship between the quantity of included bpac molecules and the completeness of the spin transition, thereby underlining the key role of the π-π stacking interactions operating between the host and guest bpac molecules within the network. Although the inclusion of the bpac molecules tends to increase the amount of active iron centers, no variation of the transition temperature was measured. We have also investigated the ability of the network to accommodate the inclusion of molecules other than water and bpac and studied the synergy between the host-guest interaction and the spin-crossover behavior. In fact, the clathration of various aromatic molecules revealed specific modifications of the transition temperature. Finally, the transition temperature and the completeness of the transition are related to the nature of the metal associated with the iron center (Ni, Pt, or Pd) and also to the nature and the amount of guest molecules in the lattice. Copyright
- Bartual-Murgui, Carlos,Salmon, Lionel,Akou, Amal,Ortega-Villar, Norma A.,Shepherd, Helena J.,Munoz, M. Carmen,Molnar, Gabor,Real, Jose Antonio,Bousseksou, Azzedine
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- Tuning supramolecular aurophilic structures: The effect of counterion, positive charge and solvent
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The synthesis of the cationic gold(i) complexes [Au(C≡CC5H4N)(CH3-PTA)]X (X = I, 1; X = OTf, 4), [Au(C≡CC5H4N-CH3)(PTA)]X (X = I, 2; X = OTf = 5; PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane) and [Au(C≡CC5H4N-CH3)(DAPTA)]X (X = I, 3; X = OTf = 6, DAPTA = 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) results in cationic complexes with unexpected supramolecular assemblies in water ranging from rod-like structures (1) to vesicles (2 and 3) and square-like structures (5 and 6). These morphologies are completely different from the fibers previously obtained with their parent neutral complexes [Au(C≡C5H4N)(PTA)] and [Au(C≡C5H4N)(DAPTA)]. Nevertheless, the introduction of triflate as a counterion in 1 (complex 4) gives rise to the formation of a highly soluble complex in water which does not display any significant aggregation in solution. These results reveal the importance of the introduction of a positive charge on global supramolecular assemblies and how the counterion can also modify the resulting package. Interestingly, we have also proved that the aggregation of complexes 2, 3, 5 and 6 is also affected by the solvent with direct influence on their absorption and emission properties and the global morphology of the aggregates.
- Aguiló, Elisabet,Gavara, Raquel,Baucells, Clara,Guitart, Marta,Lima, Jo?o Carlos,Llorca, Jordi,Rodríguez, Laura
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- Synthesis, Electrochemistry, and Optical Properties of Highly Conjugated Alkynyl-Ferrocenes and -Biferrocenes
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Sonogashira reactions are utilized herein to react iodo-ferrocenes and -biferrocenes with terminal alkyne ligands, functionalized with both pyridine and thioanisole groups. High-yielding reactions generate both monoalkynyl and dialkynyl derivatives, the r
- Bennett, Troy L. R.,Wilkinson, Luke A.,Lok, Jasmine M. A.,O'Toole, Robert C. P.,Long, Nicholas J.
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p. 1156 - 1162
(2021/05/06)
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- Design and characterization of a heterocyclic electrophilic fragment library for the discovery of cysteine-targeted covalent inhibitors
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A fragment library of electrophilic small heterocycles was characterized through cysteine-reactivity and aqueous stability tests that suggested their potential as covalent warheads. The analysis of theoretical and experimental descriptors revealed correlations between the electronic properties of the heterocyclic cores and their reactivity against GSH that are helpful in identifying suitable fragments for cysteines with specific nucleophilicity. The most important advantage of these fragments is that they show only minimal structural differences from non-electrophilic counterparts. Therefore, they could be used effectively in the design of targeted covalent inhibitors with minimal influence on key non-covalent interactions.
- Keeley,ábrányi-Balogh,Keseru
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p. 263 - 267
(2019/03/05)
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- Synthesis, optical spectroscopy, structural, and DFT studies on dimeric iodo-bridged Copper(I)complexes
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Three new iodo-bridged copper(I)complexes of the type [CuI(PPh3)L]2, where L = Ar–≡–C5H4N, Ar = phenyl (C1), biphenyl (C2)and flourenyl (C3)have been synthesized via coordination-driven self-assembly processes. Two of Cu(I)complexes, C2 and C3, have been characterized by single-crystal X-ray diffraction studies. The complexes have two molecules of the P-donor ligand and two molecules of the N-donor ligand in trans configurations, supporting the central Cu2I2 unit. Absorption properties of the complexes have been investigated. Extensive DFT calculation has been carried out to delineate the influence of aromatic spacers on the optical properties and the nature of excited states. The ease of synthesis of these Cu(I)dimers and the wide range of ethynylpyridine supporting ligands that can be incorporated highlights the potential for these materials to form polymers by linking through the ethylylpyridine ligands.
- Haque, Ashanul,Al Balushi, Rayya A.,Al-Busaidi, Idris Juma,Ilmi, Rashid,Al Rasbi, Nawal,Jayapal, Maharaja,Khan, Muhammad S.,Raithby, Paul R.
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- INHIBITORS FOR THE Β-CATENIN / T-CELL FACTOR PROTEIN–PROTEIN INTERACTION
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Disclosed are inhibitors for the β-catenin/T-cell factor interaction. The inhibitors are selective for β-catenin/T-cell factor over β-catenin/cadherin and β-catenin/APC interactions. Methods of using the disclosed compounds to treat cancer are also disclosed.
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Page/Page column 37; 38
(2019/10/23)
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- SO2F2-Mediated Oxidative Dehydrogenation and Dehydration of Alcohols to Alkynes
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Direct synthesis of alkynes from inexpensive, abundant alcohols was achieved in high yields (greater than 40 examples, up to 95% yield) through a SO2F2-promoted dehydration and dehydrogenation process. This straightforward transformation of sp3-sp3 (C-C) bonds to sp-sp (C=C) bonds requires only inexpensive and readily available reagents (no transition metals) under mild conditions. The crude alkynes are sufficiently free of impurities to permit direct use in further transformations, as illustrated by regioselective Huisgen alkyne-azide cycloaddition reactions with PhN3 to give 1,4-substituted 1,2,3-traiazoles (16 examples, up to 92% yield) and Sonogashira couplings (10 examples, up to 77% yield).
- Zha, Gao-Feng,Fang, Wan-Yin,Li, You-Gui,Leng, Jing,Chen, Xing,Qin, Hua-Li
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supporting information
p. 17666 - 17673
(2019/01/04)
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- Chemistry of 4-[(4-bromophenyl)ethynyl]pyridine at metal surfaces studied by STM
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Molecular architectures (Kagome networks, coordinated/covalent dimers and branched coordination chains) via self-assembly, Ullmann reaction and pyridine coordination of 4-[(4-bromophenyl)ethynyl]pyridine are found to be sensitive to the underlying metallic surfaces. The molecular species were characterised on the surface by low-temperature scanning tunnelling microscopy (LT-STM) at sub-molecular level.
- Ren, Jindong,Larkin, Eugene,Delaney, Colm,Song, Yang,Jin, Xin,Amirjalayer, Saeed,Bakker, Anne,Du, Shixuan,Gao, Hongying,Zhang, Yu-Yang,Draper, Sylvia M.,Fuchs, Harald
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p. 9305 - 9308
(2018/08/29)
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- Dicopper(I) Complexes Incorporating Acetylide-Functionalized Pyridinyl-Based Ligands: Synthesis, Structural, and Photovoltaic Studies
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Heteroaryl incorporated acetylide-functionalized pyridinyl ligands (L1-L6) with the general formula Py-C≡C-Ar (Py = pyridine and Ar = thiophene-2-yl, 2,2′-bithiophene]-5-yl, 2,2′:5′,2″-terthiophene]-5-yl, thieno[2,3-b]thiophen-2-yl, quinoline-5-yl, benzo[c][1,2,5]thiadiazole-5-yl) have been synthesized by Pd(0)/Cu(I)-catalyzed cross-coupling reaction of 4-ethynylpyridine and the respective heteroaryl halide. Ligands L1-L6 were isolated in respectable yields and characterized by microanalysis, IR spectroscopy, 1H NMR spectroscopy, and ESI-MS mass spectrometry. A series of dinuclear Cu(I) complexes 1-10 have been synthesized by reacting L1-L6 with CuI and triphenylphosphine (PPh3) (R1) or with an anchored phosphine derivative, 4-(diphenylphosphino) benzoic acid (R2)/2-(diphenylphosphino)benzenesulfonic acid (R3), in a stoichiometric ratio. The complexes are soluble in common organic solvents and have been characterized by analytical, spectroscopic, and computational methods. Single-crystal X-ray structure analysis confirmed rhomboid dimeric structures for complexes 1, 2, 4, and 5, and a polymeric structure for 6. Complexes 1-6 showed oxidation potential responses close to 0.9 V vs Fc0/+, which were chemically irreversible and are likely to be associated with multiple steps and core oxidation. Preliminary photovoltaic (PV) results of these new materials indicated moderate power conversion efficiency (PCE) in the range of 0.15-1.56% in dye-sensitized solar cells (DSSCs). The highest PCE was achieved with complex 10 bearing the sulfonic acid anchoring functionality.
- Jayapal, Maharaja,Haque, Ashanul,Al-Busaidi, Idris J.,Al-Rasbi, Nawal,Al-Suti, Mohammed K.,Khan, Muhammad S.,Al-Balushi, Rayya,Islam, Shahidul M.,Xin, Chenghao,Wu, Wenjun,Wong, Wai-Yeung,Marken, Frank,Raithby, Paul R.
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p. 12113 - 12124
(2018/09/27)
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- Supramolecular Chemistry of Some Metal Acetylacetonates with Auxiliary Pyridyl Sites
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Hetero-bifunctional ligands can pave the way for elaborate metallo-supramolecular systems and are also useful for combining metal-ligand bonding with other types of noncovalent interactions. We synthesized two new pyridyl-acetylacetonate ligands, 3-(4-(pyridin-4-yl)phenyl)pentane-2,4-dione (L1) and 3-(4-(pyridin-4-ylethynyl)phenyl)pentane-2,4-dione (L2), and explored their metal binding ability with selected di- and trivalent transition metal ions. As expected, the acetylacetonate ligation with metal dications remains consistent among four structures, [Cu(L1)2(MeOH)2]n, [Co(L2)2]n, [Cu(L2)2(MeOH)2], and [Zn(L2)2(MeOH)2]; the metal is four-coordinate and resides in a square planar environment. Differences in the overall architectures arise basically from the role played by the terminal heterocycle (i.e., the pyridyl group). In [Cu(L1)2(MeOH)2]n and [Co(L2)2]n, the heterocyclic end directly binds to the metal (through vacant axial positions), thereby producing coordination networks. In [Cu(L2)2(MeOH)2] and [Zn(L2)2(MeOH)2], metal-methanol coordination and intermolecular O-H(methanol)···N(pyridine) hydrogen-bond interactions work in concert to weave those bis-acetylacetonate complexes into ribbon-like supramolecular polymeric arrays. Somewhat surprisingly, the only tris-chelated acetylacetonate complex characterized in this study, [Fe(L2)3], essentially exists as discrete dimeric aggregates.
- Gunawardana, Chamara A.,Sinha, Abhijeet S.,Desper, John,Lakovi?, Marijana,Aaker?y, Christer B.
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p. 6936 - 6945
(2018/10/20)
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- Self-assembling molecular capsules based on α,γ-cyclic peptides
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A new capsule based on a β-sheet self-assembling cyclic peptide with the ability to recognize and release several guests is described. The host structure is composed of two self-complementary α,γ-cyclic peptides bearing a Zn porphyrin cap that is used for the selective recognition of the guest. The two components are linked through two dynamic covalent bonds. The combination of binding forces, including hydrogen bonding, metal coordination, and dynamic hydrazone bonds, allows the reversible recognition of long bipyridine guests. The affinity for these ligands showed a strong dependence on the guest length. Delivery of the encapsulated ligand can be achieved by hydrolysis of hydrazones to disrupt the sandwich complex structure.
- Ozores, Haxel Lionel,Amorín, Manuel,Granja, Juan R.
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p. 776 - 784
(2017/05/17)
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- PYRAZOLE DERIVATIVES
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Provided herein are compounds of the formula I: as well as pharmaceutically acceptable salts thereof, wherein the substituents are as those disclosed in the specification. These compounds, and the pharmaceutical compositions containing them, are useful for the treatment or prevention of mGluR5 mediated disorders, such as acute and/or chronic neurological disorders, cognitive disorders and memory deficits, as well as acute and chronic pain.
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- PYRROLE DERIVATIVES
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Provided herein are compounds of the formula (I) : as well as pharmaceutically acceptable salts thereof, wherein the substituents are as those disclosed in the specification. These compounds, and the pharmaceutical compositions containing them, are useful
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- Heterocyclic compounds, comprising of organic light-emitting device and organic light emitting display
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Heterocyclic compounds, synthetic methods for preparing the same, and organic light-emitting display devices comprising the same are described. The subject heterocyclic compounds may comprise an aromatic ring or a heteroaromatic ring fused with a carbazole, dibenzothiophene, or dibenzofurane derivative, the compounds featuring rigid backbone structures with high glass transition temperatures and high melting points. The subject heterocyclic compounds may exhibit high electrical stability, improved charge transport ability, high heat resistance and improved light-emitting properties when used in organic light-emitting devices. Organic light-emitting display devices prepared according to the present invention exhibit lower driving voltages, increased luminescent efficiencies and longer lifetimes.
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Paragraph 0300; 0324-0328
(2017/09/13)
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- Heterocyclic compound and organic light-emitting device including the same
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A heterocyclic compound is represented by Formula 1. An organic light emitting device includes a first electrode, a second electrode and an organic layer between the first and second electrodes. The organic layer includes the heterocyclic compound. An org
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Page/Page column 61-62; 64
(2016/08/07)
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- DOSY NMR, X-ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M6L4 Coordination Cages
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A novel modular approach to electron-deficient and electron-rich M6L4 cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two C3-symmetric ligands L1 and L2 with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand L1 is more electron-deficient than the well-known 2,4,6-tri(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand L2 is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)Pt(OTf)2] or [(dppp)Pd(OTf)2] corner-complexes yields two electron-deficient (1a and 1b) and two electron-rich (2a and 2b) M6L4 cages. The single crystal X-ray diffraction study of 1a and 2a confirms the expected octahedral shape with a ca. 2000 ?3 cavity and ca. 11 ? wide apertures. The crystallographically determined diameters of 1a and 2a are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl3:CD3OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt6L4 and Pd6L4 cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands L1 and L2 and cages 1a, 1b, 2a, and 2b were studied by UV-vis and fluorescence spectroscopy.
- Bonakdarzadeh, Pia,Topi?, Filip,Kalenius, Elina,Bhowmik, Sandip,Sato, Sota,Groessl, Michael,Knochenmuss, Richard,Rissanen, Kari
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p. 6055 - 6061
(2015/06/25)
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- Structure-based design, synthesis and evaluation in vitro of arylnaphthyridinones, arylpyridopyrimidinones and their tetrahydro derivatives as inhibitors of the tankyrases
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Abstract The tankyrases are members of the PARP superfamily; they poly(ADP-ribosyl)ate their target proteins using NAD+ as a source of electrophilic ADP-ribosyl units. The three principal protein substrates of the tankyrases (TRF1, NuMA and axin) are involved in replication of cancer cells; thus inhibitors of the tankyrases may have anticancer activity. Using structure-based drug design and by analogy with known 3-arylisoquinolin-1-one and 2-arylquinazolin-4-one inhibitors, series of arylnaphthyridinones, arylpyridinopyrimidinones and their tetrahydro-derivatives were synthesised and evaluated in vitro. 7-Aryl-1,6-naphthyridin-5-ones, 3-aryl-2,6-naphthyridin-1-ones and 3-aryl-2,7-naphthyridin-1-ones were prepared by acid-catalysed cyclisation of the corresponding arylethynylpyridinenitriles or reaction of bromopyridinecarboxylic acids with β-diketones, followed by treatment with NH3. The 7-aryl-1,6-naphthyridin-5-ones were methylated at 1-N and reduced to 7-aryl-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-ones. Cu-catalysed reaction of benzamidines with bromopyridinecarboxylic acids furnished 2-arylpyrido[2,3-d]pyrimidin-4-ones. Condensation of benzamidines with methyl 1-benzyl-4-oxopiperidine-3-carboxylate and deprotection gave 2-aryl-5,6,7,8-tetrahydropyrido[4,3-d]pyrimidin-4-ones, aza analogues of the known inhibitor XAV939. Introduction of the ring-N in the arylnaphthyridinones and the arylpyridopyrimidinones caused >1000-fold loss in activity, compared with their carbocyclic isoquinolinone and quinazolinone analogues. However, the 7-aryl-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-ones showed excellent inhibition of the tankyrases, with some examples having IC50 = 2 nM. One compound (7-(4-bromophenyl)-1-methyl-1,2,3,4-tetrahydro-1,6-naphthyridin-5-one) showed 70-fold selectivity for inhibition of tankyrase-2 versus tankyrase-1. The mode of binding was explored through crystal structures of inhibitors in complex with tankyrase-2.
- Kumpan, Katerina,Nathubhai, Amit,Zhang, Chenlu,Wood, Pauline J.,Lloyd, Matthew D.,Thompson, Andrew S.,Haikarainen, Teemu,Lehti?, Lari,Threadgill, Michael D.
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supporting information
p. 3013 - 3032
(2015/08/03)
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- "quick and click" assembly of functionalised indole rings via metal-promoted cyclative tandem reactions
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An efficient and convenient synthesis of a variety of decorated indoles using a three-component tandem metal-catalysed process is described. We propose here a new "synthetic kit" that allows for the "quick and click" assembly of indole rings using readily available, and inexpensive starting materials under environmentally friendly reaction conditions. This journal is
- Capitta, Francesca,De Luca, Lidia,Porcheddu, Andrea
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p. 59297 - 59301
(2015/02/19)
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- Zinc porphyrins with a pyridine-ring-anchoring group for dye-sensitized solar cells
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Anchoring groups are extremely important in controlling the performance of dye-sensitized solar cells (DSCs). The design and characterization of sensitizers with new anchoring groups, in particular non-carboxylic acid groups, has become a recent focus of DSC research. Herein, new donor-p-acceptor zinc-porphyrin dyes with a pyridine ring as an anchoring group have been designed and synthesized for applications in DSCs. Photophysical and electrochemical investigations demonstrated that the pyridine ring worked effectively as an anchoring group for the porphyrin sensitizers. DSCs that were based on these new porphyrins showed an overall powerconversion efficiency of about 4.0% under full sunlight (AM 1.5G, 100 mWcm-2).
- Lu, Jianfeng,Xu, Xiaobao,Li, Zhihong,Cao, Kun,Cui, Jin,Zhang, Yibo,Shen, Yan,Li, Yi,Zhu, Jun,Dai, Songyuan,Chen, Wei,Cheng, Yibing,Wang, Mingkui
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supporting information
p. 956 - 962
(2013/08/25)
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- Novel iron(II) microporous spin-crossover coordination polymers with enhanced pore size
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In this Communication, we report the synthesis and characterization of novel Hofmann-like spin-crossover porous coordination polymers of composition {Fe(L)[M(CN)4]}·G [L = 1,4-bis(4-pyridylethynyl)benzene and MII = Ni, Pd, and Pt]. The spin-crossover properties of the framework are closely related to the number and nature of the guest molecules included in the pores.
- Mu?oz-Lara, Francisco J.,Gaspar, Ana B.,Mu?oz, M. Carmen,Ksenofontov, Vadim,Real, José Antonio
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supporting information
p. 3 - 5
(2013/02/23)
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- Single-molecule conductance of functionalized oligoynes: Length dependence and junction evolution
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We report a combined experimental and theoretical investigation of the length dependence and anchor group dependence of the electrical conductance of a series of oligoyne molecular wires in single-molecule junctions with gold contacts. Experimentally, we focus on the synthesis and properties of diaryloligoynes with n = 1, 2, and 4 triple bonds and the anchor dihydrobenzo[b]thiophene (BT). For comparison, we also explored the aurophilic anchor group cyano (CN), amino (NH2), thiol (SH), and 4-pyridyl (PY). Scanning tunneling microscopy break junction (STM-BJ) and mechanically controllable break junction (MCBJ) techniques are employed to investigate single-molecule conductance characteristics. The BT moiety is superior as compared to traditional anchoring groups investigated so far. BT-terminated oligoynes display a 100% probability of junction formation and possess conductance values which are the highest of the oligoynes studied and, moreover, are higher than other conjugated molecular wires of similar length. Density functional theory (DFT)-based calculations are reported for oligoynes with n = 1-4 triple bonds. Complete conductance traces and conductance distributions are computed for each family of molecules. The sliding of the anchor groups leads to oscillations in both the electrical conductance and the binding energies of the studied molecular wires. In agreement with experimental results, BT-terminated oligoynes are predicted to have a high electrical conductance. The experimental attenuation constants βH range between 1.7 nm-1 (CN) and 3.2 nm-1 (SH) and show the following trend: β H(CN) H(NH2) H(BT) H(PY) ≈ βH(SH). DFT-based calculations yield lower values, which range between 0.4 nm -1 (CN) and 2.2 nm-1 (PY).
- Moreno-Garcia, Pavel,Gulcur, Murat,Manrique, David Zsolt,Pope, Thomas,Hong, Wenjing,Kaliginedi, Veerabhadrarao,Huang, Cancan,Batsanov, Andrei S.,Bryce, Martin R.,Lambert, Colin,Wandlowski, Thomas
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p. 12228 - 12240
(2013/09/23)
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- The photophysics of pyridine-derivatized ortho-, meta-, and para-dibutylamino cruciforms
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The photophysical properties of a series of para-substituted donor-acceptor cruciform fluorophores (p1-4) were investigated and compared with their meta and ortho isomers (m1-4 and o1-4). The structural variations were found to have a significant effect o
- Hinderer, Florian,Bunz, Uwe H. F.
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supporting information
p. 8490 - 8496
(2013/07/19)
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- Rapid discovery of a novel series of Abl kinase inhibitors by application of an integrated microfluidic synthesis and screening platform
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Drug discovery faces economic and scientific imperatives to deliver lead molecules rapidly and efficiently. Using traditional paradigms the molecular design, synthesis, and screening loops enforce a significant time delay leading to inefficient use of data in the iterative molecular design process. Here, we report the application of a flow technology platform integrating the key elements of structure-activity relationship (SAR) generation to the discovery of novel Abl kinase inhibitors. The platform utilizes flow chemistry for rapid in-line synthesis, automated purification, and analysis coupled with bioassay. The combination of activity prediction using Random-Forest regression with chemical space sampling algorithms allows the construction of an activity model that refines itself after every iteration of synthesis and biological result. Within just 21 compounds, the automated process identified a novel template and hinge binding motif with pIC50 > 8 against Abl kinase - both wild type and clinically relevant mutants. Integrated microfluidic synthesis and screening coupled with machine learning design have the potential to greatly reduce the time and cost of drug discovery within the hit-to-lead and lead optimization phases.
- Desai, Bimbisar,Dixon, Karen,Farrant, Elizabeth,Feng, Qixing,Gibson, Karl R.,Van Hoorn, Willem P.,Mills, James,Morgan, Trevor,Parry, David M.,Ramjee, Manoj K.,Selway, Christopher N.,Tarver, Gary J.,Whitlock, Gavin,Wright, Adrian G.
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supporting information
p. 3033 - 3047
(2013/05/22)
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- L-shaped benzimidazole fluorophores: Synthesis, characterization and optical response to bases, acids and anions
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Nine L-shaped benzimidazole fluorophores have been synthesized, computationally evaluated and spectroscopically characterized. These "half-cruciform" fluorophores respond to bases, acids and anions through changes in fluorescence that vary from moderate t
- Lirag, Rio Carlo,Le, Ha T. M.,Miljanic, Ognjen S.
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p. 4304 - 4306
(2013/06/05)
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- MOLECULAR CARTESIAN-COORDINATE PLATFORMS
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A compound of formula MOL -M-L, wherein M is a 5 or 6-coordinate metal, L is a bidentate ligand, and MOL is a compound of formula (II) : (II) wherein X is C and R\ R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are as defined herein. In another embodime
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Page/Page column 72
(2012/10/18)
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- Clickable inverse opal: A useful platform for fabrication of stimuli-responsive photonic materials
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Based on azide-containing clickable inverse opal, a strategy for efficiently fabricating functional photonic materials was developed. By using three types of ethynylated compounds as model molecules, it is found that different functional groups can be facilely introduced into the prepared inverse opal via click reaction to access various inverse opaline materials.
- Xu, Dan,Zhu, Wei,An, Qi,Li, Weina,Li, Xuesong,Yang, Haowei,Yin, Jinxiang,Li, Guangtao
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supporting information; experimental part
p. 3494 - 3496
(2012/06/18)
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- Pd-catalyzed [2+2+1] coupling of alkynes and arenes: Phenol diazonium salts as mechanistic trapdoors
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Alkynes and phenol diazonium salts undergo a Pd-catalyzed [2+2+1] cyclization reaction to spiro[4,5]decatetraene-7-ones. This structure was confirmed for one example by X-ray single-crystal structure analysis. The reaction is believed to proceed through oxidative addition of the phenol diazonium cation to Pd0, subsequent insertion of two alkynes, followed by irreversible spirocyclization. Copyright
- Schmidt, Bernd,Berger, Rene,Kelling, Alexandra,Schilde, Uwe
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supporting information; experimental part
p. 7032 - 7040
(2011/07/30)
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- Benzobisoxazole cruciforms: Heterocyclic fluorophores with spatially separated frontier molecular orbitals
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We report the synthesis of nine conjugated cruciform-shaped molecules based on the central benzo[1,2-d:4,5-d′]bisoxazole nucleus, at which two conjugated currents intersect at a ~90° angle. Cruciforms' substituents were varied pairwise among the electron-
- Lim, Jaebum,Albright, Thomas A.,Martin, Benjamin R.,Miljanic, Ognjen S.
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experimental part
p. 10207 - 10219
(2012/02/03)
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- Synthesis of dihydroindolizines for potential photoinduced work function alteration
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Seeking to immobilize photochromophores on metallic surfaces, we have synthesized four molecules which contain both a photoresponsive dihydroindolizine (DHI) core and a sulfur containing moiety, which allow for their assembly onto gold substrates. Sonogashira, Suzuki, or Ullmann couplings are employed to generate pyridines with pendant thioacetates (or disulfides). The pyridines are condensed with spiro[2-cyclopropene-1, 9′-[9H]fluorene]- 2, 3-dimethyl ester affording the targeted DHIs.
- Bartucci, Matthew A.,Wierzbicki, Patrycja M.,Gwengo, Chengeto,Shajan, Sunny,Hussain, Syed H.,Ciszek, Jacob W.
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p. 6839 - 6842
(2011/03/18)
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- A novel potent nicotinamide phosphoribosyltransferase inhibitor synthesized via click chemistry
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The inhibition of NAD synthesis or salvage pathways has been proposed as a novel target for antitumoral drugs. Two molecules with this mechanism of action are at present undergoing clinical trials. In searching for similar novel molecules, we exploited co
- Colombano, Giampiero,Travelli, Cristina,Galli, Ubaldina,Caldarelli, Antonio,Chini, Maria Giovanna,Canonico, Pier Luigi,Sorba, Giovanni,Bifulco, Giuseppe,Tron, Gian Cesare,Genazzani, Armando A.
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supporting information; experimental part
p. 616 - 623
(2010/07/06)
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- Inhibitors of HIV-1 reverse transcriptase
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The present invention provides compounds for treating or preventing an HIV infection, or treating AIDS or ARC comprising administering a compound according to Formulae I and II wherein Q, R1, R2, and R3 are defined as described herein.
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Page/Page column 19
(2010/04/23)
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- Synthesis of conjugated (1E,3E)- and (1Z,3Z)-1,4-di(n-pyridyl) (or n-quinolyl)-1,3-butadienes from n-(2′-chloroethenyl)pyridine (or quinoline)
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The homocoupling reaction between the conjugated n-(2-chloroethenyl)pyridine; n, 2-, 3- and 4- (or quinoline; n, 2- and 4-) mediated by zero-valent nickel complexes at room temperature affords to the corresponding 1,4-diaryl-1,3-butadiene, always as the 1E,3E stereoisomer. The yield in 1,4-diaryl-1,3-butadiene increases with the nickel catalyst and hence, the active zero-valent nickel catalyst is not regenerated during the homocoupling reaction. The stereospecific synthesis of (1Z,3Z)-1,4-di(4′-pyridyl)-1,3-butadiene stereoisomer was efficiently carried out by partial hydrogenation of the appropriate 1,4-di(4′-pyridyl)-1,3-butadiyne.
- Rodríguez,Díaz-Oliva, Cristina
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experimental part
p. 2512 - 2517
(2009/08/07)
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- 1,3-Dipolar cycloaddition of alkynes to azides. Construction of operationally functional metal responsive fluorophores
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The copper catalyzed 1,3-dipolar cycloaddition of 4-butoxyphenylazide with 2-, 3- or 4-ethynylpyridine furnishes 1,4-diaryltriazoles, which display turn-on fluorescence upon addition of metal cations. The Royal Society of Chemistry.
- Schweinfurth, David,Hardcastle, Kenneth I.,Bunz, Uwe H. F.
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p. 2203 - 2205
(2008/12/23)
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- Synthesis of meso-extended tetraarylporphyrins
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(Chemical Equation Presented) The synthesis of five new meso-tetraarylporphyrins having pyridine, pyrimidine, or nitrile groups extending tetragonally via alkynyl linkages from the para positions is described. The radial extension is nearly double that of
- Richardson, Christopher,Reed, Christopher A.
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p. 4750 - 4755
(2008/02/04)
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- New cruciform structures: Toward coordination induced single molecule switches
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(Chemical Equation Presented) New cruciform structures 1-4 were synthesized to investigate a new single molecule switching mechanism arising from the interplay between the molecule and the electrode surface. These molecular cruxes consist of two rod-type
- Grunder, Sergio,Huber, Roman,Horhoiu, Viviana,Gonzalez, Maria Teresa,Schoenenberger, Christian,Calame, Michel,Mayor, Marcel
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p. 8337 - 8344
(2008/03/11)
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- Amino-5-(6-membered)heteroarylimidazolone compounds and the use thereof for beta-secretase modulation
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The present invention provides a 2-amino-5-heteroaryl-5-phenylimidazolone compound of formula I The present invention also provides methods for the use thereof to inhibit β-secretase (BACE) and treat β-amyloid deposits and neurofibrillary tangles
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Page/Page column 11
(2008/06/13)
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- 4-Aryl-1,2,3-triazole: A novel template for a reversible methionine aminopeptidase 2 inhibitor, optimized to inhibit angiogenesis in vivo
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Inhibitors of human methionine aminopeptidase type 2 (hMetAP2) are of interest as potential treatments for cancer. A new class of small molecule reversible inhibitors of hMetAP2 was discovered and optimized, the 4-aryl-1,2,3-triazoles. Compound 24, a potent inhibitor of cobalt-activated hMetAP2, also inhibits human and mouse endothelial cell growth. Using a mouse matrigel model, this reversible hMetAP2 inhibitor was also shown to inhibit angiogenesis in vivo.
- Kallander, Lara S.,Lu, Qing,Chen, Wenfang,Tomaszek, Thaddeus,Yang, Guang,Tew, David,Meek, Thomas D.,Hofmann, Glenn A.,Schulz-Pritchard, Christina K.,Smith, Ward W.,Janson, Cheryl A.,Ryan, M. Dominic,Zhang, Gui-Feng,Johanson, Kyung O.,Kirkpatrick, Robert B.,Ho, Thau F.,Fisher, Paul W.,Mattern, Michael R.,Johnson, Randall K.,Hansbury, Michael J.,Winkler, James D.,Ward, Keith W.,Veber, Daniel F.,Thompson, Scott K.
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p. 5644 - 5647
(2007/10/03)
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- Aromatic and aromatic/heteroaromatic molecular structures with controllable electron conducting properties
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Aromatic and aromatic/heteroaromatic molecular structures with controllable electron conducting properties are derived from the incorporation of electron active substituents in selective positions.
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Page/Page column 4-5
(2008/06/13)
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- One-pot synthesis of monosubstituted aryl(hetaryl)acetylenes by direct introduction of the C≡CH residue into arenes and hetarenes
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A convenient one-pot synthesis of aryl(hetaryl)acetylenes by cross-coupling of aryl(hetaryl)iodides with acetylene in presence of PdCl2(Ph 3)2, CuI and K2CO3 in DMF has been developed.
- Vasilevsky, Sergei F.,Klyatskaya, Svetlana V.,Elguero, José
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p. 6685 - 6688
(2007/10/03)
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- TRIAZOLE DERIVATIVES AS TACHYKININ RECEPTOR ANTAGONISTS
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This application relates to a compound of Formula (I) or a pharmaceutically acceptable salt thereof, pharmaceutical compositions thereof, and its use as an inhibitor of the NK-1 subtype of tachykinin receptors, as well as a process for its preparation and intermediates therefor. (I) wherein: D is a C1-C3 alkane-diyl; R1 is phenyl, which is optionally substituted with one to three substitutents indpendently selected from the group consisting of halo, C1-C4 alkyl, C1-C4 alkoxy, cyano, difluoromethyl, trifluoromethyl, and trifluoromethoxy; R4 is a radical selected from the group consisting of: (IA), (IB), (IC), (ID), (IE), (IF), (IG), (IH)
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Page/Page column 49
(2010/02/07)
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- Efficient synthesis of a complete donor/acceptor bis(aryl)diyne family
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A facile route to a family of bis(aryl)diynes containing both an electron donating pyridine ring and an electron accepting iodobenzene has been developed. The convergent synthesis involves the coupling of 2-, 3-, or 4-bromopyridine with TMS-acetylene, followed by deprotection to form the first half of the molecule. Similarly, 2-, 3-, or 4-iodoaniline was coupled to TMS-acetylene after protection of the amine group as a diethyltriazine. After conversion of the triazine to an iodine, deprotection of the acetylene and formation of the corresponding bromophenyl-acetylene, the two halves of the molecule were coupled under Cadiot-Chodkiewicz conditions. Nine new compounds were prepared, each of which was found to thermally polymerize from the melt. None of the compounds underwent photochemical polymerization in the solid-state.
- Holmes, Brian T.,Pennington, William T.,Hanks, Timothy W.
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p. 2447 - 2461
(2007/10/03)
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- Rational syntheses of cyclic hexameric porphyrin arrays for studies of self-assembling light-harvesting systems
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Two new cyclic hexameric arrays of porphyrins have been prepared in a rational, convergent manner. The porphyrins in each cyclic hexamer are joined by diphenylethyne linkers affording a wheel-like array with a diameter of ~35 A. One array is comprised of
- Yu,Lindsey
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p. 7402 - 7419
(2007/10/03)
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- Syntheses and characterization of 1,1'-bis(3-pyridylethynyl)ferrocene and 1,1'-bis(4-pyridylethynyl)ferrocene
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Two novel disubstituted ferrocene, 1,1'-bis(3-pyridylethynyl)ferrocene 1 and 1,1'-bis(4-pyridylethynyl)ferrocene 2, were synthesized and fully characterized by elemental analysis, 1H NMR 13C NMR IR, and X-ray crystallography. Compound 1crystallizes in monoclinic, space group Cc, a=17.26?, b=9.77?, c=10.85?, β=105.45; R1 =0.0399, wR2=0.1077, GooF=1.023. The two arms of the ferrocene are parallel, which will play an important role both in the coordination chemistry and electronic communiculion of the ferrocene.
- Lindner, Ekkehard,Zong, Ruifa,Eichele, Klaus
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p. 219 - 222
(2007/10/03)
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- An improved preparation of 4-ethynylpyridine and its application to the synthesis of linear bipyridyl ligands
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A convenient synthesis of 4-ethynylpyridine, 5, starting from 4- vinylpyridine has been developed. Compound 5 reacts readily with pyridyl- and aryl-iodides to give the linear bidentate ligands 7, 9, and 11 in excellent yields.
- Champness, Neil R.,Khlobystov, Andrei N.,Majuga, Alexander G.,Schroeder, Martin,Zyk, Nikolai V.
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p. 5413 - 5416
(2007/10/03)
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- Orbital interactions in ethynylpyridines
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He I and He II photoelectron spectra of several isomeric ethynyl- and diethynylpyridines have been measured. The spectra were analyzed with the aid of empirical arguments: relative band intensities and comparison with spectra of related compounds (ethynyl
- Ng, Siu Choon,Novak, Igor,You, Xiaomei,Huang, Wei
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p. 904 - 908
(2007/10/03)
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- Synthesis of 1,4-di(n-pyridyl)buta-1,3-diyne and formation of charge-transfer complexes. X-Ray structure of 1,4-di(3-pyridyl)buta-1,3-diyne
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Ethynylpyridines have been satisfactorily prepared by two different routes: (a) the Wittig reaction between chloromethylene(triphenyl)phosphine ylide and a pyridinecarbaldehyde, followed by elimination of hydrogen chloride; (b) from the 2-methyl-4-(n-pyridyl)but-3-yn-2-ol intermediate, by elimination of acetone. 1,4-Di(n-pyridyl)buta-1,3-diynes are obtained by oxidative dimerization in good yield. An X-ray structure of the 3-substituted dimer is reported. Mono- and di-methyl salts of the 3-substituted diyne have been obtained and the charge-transfer complexes with tetramethyl-p-phenylenediamine (TMPD) are formed.
- Rodriguez, J. Gonzalo,Martin-Villamil, Rosa,Cano, Felix H.,Fonseca, Isabel
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p. 709 - 714
(2007/10/03)
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- Molecular architecture via coordination: Self-assembly, characterization, and host-guest chemistry of mixed, neutral-charged, Pt-Pt and Pt-Pd macrocyclic tetranuclear complexes. X-ray crystal structure of cyclobis[[cis-Pt(dppp)(4-ethynylpyridine)2
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Interaction of cis-Ptdppp(p-C6H4CN)2 or cis-Ptdppp(p-C2C6H4N)2 with cis-ML2(OSO2CF3)2 (M = Pt or Pd; L = PEt3 or L2/s
- Whiteford, Jeffery A.,Lu, Cuong V.,Stang, Peter J.
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p. 2524 - 2533
(2007/10/03)
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- General method for the preparation of alkyne-functionalized oligopyridine building blocks
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A large series of alkyne-substituted oligopyridines based on 2,2′-bipyridine, 1,10-phenanthroline, 2,2′:6′,2″-terpyridine, or 1,8-naphthyridine substrates has been synthesized and fully characterized. The palladium(0)-catalyzed coupling of bromo- or chloro-substituted derivatives with (trimethylsilyl)-acetylene proceeds readily in diisopropylamine under ambient conditions giving good yields of the corresponding alkyne-substituted substrates oligoPy(C≡C)SiMe3. The terminal monoynes oligoPyC≡CH become available upon treatment with K2CO3 in methanol. Stepwise homologation of the acetylene function by Cadiot-Chodkiewicz coupling of oligoPyC≡CH with (bromoethynyl)-triethylsilane (BrC≡CSiEt3) affords, in good yield, the silylated diynes oligoPy(C≡C)2SiEt3, from which the terminal diynes oligoPy(C≡C)2H are formed by treatment with aqueous methanolic alkali. Reaction of oligoPy(C≡C)2H with BrC≡CSiEt3 yields the silylated triynes oligoPy(C≡C)3SiEt3 in modest yield. Further homologation is limited by nucleophilic attack of n-propylamine at the C-2 carbon of the alkyne chain, giving rise to a mixture of cis/cis (48%), cis/trans (33%), and trans/ trans (19%) enaminediyne compounds 21a-c. Glaser oxidative self-coupling of the terminal diynes provides access to ditopic bipyridine or terpyridine ligands oligoPy(C≡C)4oligoPy comprising a tetrayne spacer. Quantitative formation of air-stable copper(I) complexes is described for the 6,6′-substituted ligands. A single crystal X-ray structure of complex 22a shows that the two ligands are interlocked around the copper(I) center in a pseudotetrahedral arrangement, similar to the structure deduced from NMR and FAB+ data. The synthetic methods reported herein represent a valuable approach to the large-scale preparation of alkyne-functionalized oligopyridines.
- Ziessel, Raymond,Suffert, Jean,Youinou, Marie-Therese
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p. 6535 - 6546
(2007/10/03)
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