- Synthesis and performances of poly(butylene-succinate) with enhanced viscosity and crystallization rate via introducing a small amount of diacetylene groups
-
A cross-linkable comonomer containing a diacetylene group, named dimethyl 4,4′-(buta-1,3-diyne-1,4-diyl)dibenzoate (DA) was synthesized and copolymerized with dimethyl succinate and 1,4-butanediol to prepare a series of slightly cross-linked PBS copolyesters (PBDASx). The chemical structure, crystallization and rheological behaviours of PBDASx were well investigated. Compared to neat PBS, PBDASx showed the greatly increased crystallization rate because of the promoting nucleation of the cross-linking domains, and the XRD results indicated that it had no influence on crystallization structure of PBS. The rheological behaviours indicate that PBDASx possessed higher viscosity than neat PBS even at high shear rate and temperature. PBDAS0.3 exhibited better comprehensive properties than neat PBS, which will widen applications of PBS.
- Liu, Gui-Cheng,Zhang, Wen-Qiang,Wang, Xiu-Li,Wang, Yu-Zhong
-
-
Read Online
- Water-Stable Zirconium-Based Metal–Organic Framework Material with High-Surface Area and Gas-Storage Capacities
-
We designed, synthesized, and characterized a new Zr-based metal–organic framework material, NU-1100, with a pore volume of 1.53 ccg?1and Brunauer–Emmett–Teller (BET) surface area of 4020 m2g?1; to our knowledge, currently the highest published for Zr-based MOFs. CH4/CO2/H2adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g?1, which corresponds to 43 g L?1. The volumetric and gravimetric methane-storage capacities at 65 bar and 298 K are approximately 180 vSTP/v and 0.27 g g?1, respectively.
- Gutov, Oleksii V.,Bury, Wojciech,Gomez-Gualdron, Diego A.,Krungleviciute, Vaiva,Fairen-Jimenez, David,Mondloch, Joseph E.,Sarjeant, Amy A.,Al-Juaid, Salih S.,Snurr, Randall Q.,Hupp, Joseph T.,Yildirim, Taner,Farha, Omar K.
-
-
Read Online
- Synthesis of a novel unsymmetrical Zn(ii) phthalocyanine bearing a phenyl ethynyl moiety as sensitizer for dye-sensitized solar cells
-
A new unsymmetrical zinc phthalocyanine sensitizer has been synthesised. The anchoring of the molecule to nanocrystalline TiO2 films is realised by a carboxylic group connected to a phenyl ethynyl moiety. Density Functional Theory (DFT) calculations show significant and positive effects of such a functionalization. Electron injection into the semiconductor and photocurrent generation in DSSC are also presented.
- Zanotti, Gloria,Angelini, Nicola,Paoletti, Anna Maria,Pennesi, Giovanna,Rossi, Gentilina,Bonapasta, Aldo Amore,Mattioli, Giuseppe,Di Carlo, Aldo,Brown, Thomas M.,Lembo, Angelo,Reale, Andrea
-
-
Read Online
- Inner salt-shaped small molecular photosensitizer with extremely enhanced two-photon absorption for mitochondrial-targeted photodynamic therapy
-
Herein, we experimentally and theoretically demonstrate an unprecedentedly enhanced two-photon absorption in a small organic molecule by a simple introduction of an inner salt-shaped structure. Moreover, such an inner salt-shaped small molecule also exhibits superior singlet oxygen quantum yield and fascinating structure-inherent mitochondrial-targeting ability for highly efficient two-photon photodynamic therapy via a mitochondrial apoptosis pathway.
- Hu, Wenbo,He, Tingchao,Jiang, Rongcui,Yin, Jun,Li, Lin,Lu, Xiaomei,Zhao, Hui,Zhang, Lei,Huang, Ling,Sun, Handong,Huang, Wei,Fan, Quli
-
-
Read Online
- Chemistry and spectroscopy of cross-conjugated and pseudo-cross-conjugated quinolinium-ethynyl-benzoate mesomeric betaines
-
The three isomers 1-methylquinolinium-2-, 3-, and 4-ethynyl(phenyl-4-carboxylates) belong to two distinct types of heterocyclic mesomeric betaines. The quinolinium substituted in position 3 is a cross-conjugated mesomeric betaine (CCMB), whereas the quinolinium derivatives substituted in positions 2 and 4 are members of the class of pseudo-cross-conjugated mesomeric betaines (PCCMBs). While the charges are strictly separated within the common π-electron system of the CCMB according to the canonical formulae, the charges are effectively but not exclusively delocalized in the PCCMBs because cumulenoid resonance forms including electron sextet structures without external octet stabilization can be formed in accordance with the definition of PCCMBs. As a consequence, despite being closely related structures, the three isomers differ in their chemical and spectroscopic behaviors. Thus, on trying to hydrolyze the ester group of the methyl quinolinium-2-ethynyl-benzoate into the corresponding acid by subsequent treatment with sodium hydroxide in methanol and aqueous hydrochloric acid at pH 3, the acetal methyl 1,1-dimethoxy-2-(quinolinium-ylidene)ethyl]benzoate and the corresponding β-enamino carbonyl compound were formed, respectively. The corresponding acids of the 2- and 4-substituted quinolinium-ethynyl-benzoates were obtained by a modified procedure. On deprotonation, the resulting cross-conjugated quinolinium-3-ethynyl-benzoate betaine proved to be stable, whereas the corresponding pseudo-cross-conjugated quinolinium-2- and -4-ethynyl-benzoate betaines decomposed. Frontier orbital profiles were calculated, and IR and Raman spectra of the starting materials were measured and calculated to analyze the differences of CCMBs and PCCMBs of mesomeric betaines possessing triple bonds. A higher contribution of the cumulenoid resonance forms to the overall structure of the PCCMBs was determined.
- Batsyts, Sviatoslav,Ramírez, Francisco J.,Casado, Juan,Namyslo, Jan C.,Schmidt, Andreas
-
-
Read Online
- Nanoscale Ln(III)-Carboxylate coordination polymers (Ln = Gd, Eu, Yb): Temperature-controlled guest encapsulation and light harvesting
-
We report the self-assembly of stable nanoscale coordination polymers (NCPs), which exhibit temperature-controlled guest encapsulation and release, as well as an efficient light-harvesting property. NCPs are obtained by coordination-directed organization of π-conjugated dicarboxylate (L1) and lanthanide metal ions Gd(III), Eu(III), and Yb(III) in a DMF system. Guest molecules trans-4-styryl-1-methylpyridiniumiodide (D1) and methylene blue (D2) can be encapsulated into NCPs, and the loading amounts can be controlled by changing reaction temperatures. Small angle X-ray diffraction (SAXRD) results reveal that the self-assembled discus-like NCPs exhibit long-range ordered structures, which remain unchanged after guest encapsulations. Experimental results reveal that the negatively charged local environment around the metal connector is the driving force for the encapsulation of cationic guests. The D1 molecules encapsulated in NCPs at 140 °C can be released gradually at room temperature in DMF. Guest-loaded NCPs exhibit efficient light harvesting with energy transfer from the framework to the guest D1 molecule, which is studied by photoluminescence and fluorescence lifetime decays. This coordination-directed encapsulation approach is general and should be extended to the fabrication of a wide range of multifunctional nanomaterials.
- Zhang, Xuanjun,Ballem, Mohamed Ali,Ahren, Maria,Suska, Anke,Bergman, Peder,Uvdal, Kajsa
-
-
Read Online
- Highly selective room temperature acetylene sorption by an unusual triacetylenic phosphine MOF
-
The new ligand tris(p-carboxyphenylethynyl)phosphine (P{CCC6H4-4-CO2H}3) was used to synthesize a permanently porous Mn(ii)-based acetylenic phosphine coordination material, PCM-48. This triply-interpenetrated MOF contains 1-D microchannels that are decorated with electron-rich and adsorbate-accessible acetylenic moieties and phosphine lone pairs. PCM-48 has a moderate room-temperature C2H2 adsorption capacity (25.54 cm3 g-1) and displays high separation selectivities for C2H2 over CH4 (C2H2/CH4 = 23.3), CO2 (C2H2/CO2 = 4.3), and N2 (C2H2/N2 = 76.9) at 296 K.
- Reynolds, Joseph E.,Walsh, Kelly M.,Li, Bin,Kunal, Pranaw,Chen, Banglin,Humphrey, Simon M.
-
-
Read Online
- Discovery of 5-{2-[5-Chloro-2-(5-ethoxyquinoline-8-sulfonamido)phenyl]ethynyl}-4-methoxypyridine-2-carboxylic Acid, a Highly Selective in Vivo Useable Chemical Probe to Dissect MCT4 Biology
-
Due to increased lactate production during glucose metabolism, tumor cells heavily rely on efficient lactate transport to avoid intracellular lactate accumulation and acidification. Monocarboxylate transporter 4 (MCT4/SLC16A3) is a lactate transporter that plays a central role in tumor pH modulation. The discovery and optimization of a novel class of MCT4 inhibitors (hit 9a), identified by a cellular screening in MDA-MB-231, is described. Direct target interaction of the optimized compound 18n with the cytosolic domain of MCT4 was shown after solubilization of the GFP-tagged transporter by fluorescence cross-correlation spectroscopy and microscopic studies. In vitro treatment with 18n resulted in lactate efflux inhibition and reduction of cellular viability in MCT4 high expressing cells. Moreover, pharmacokinetic properties of 18n allowed assessment of lactate modulation and antitumor activity in a mouse tumor model. Thus, 18n represents a valuable tool for investigating selective MCT4 inhibition and its effect on tumor biology.
- Heinrich, Timo,Sala-Hojman, Ada,Ferretti, Roberta,Petersson, Carl,Minguzzi, Stefano,Gondela, Andrzej,Ramaswamy, Shivapriya,Bartosik, Anna,Czauderna, Frank,Crowley, Lindsey,Wahra, Pamela,Schilke, Heike,B?pple, Pia,Dudek, ?ukasz,Le?, Marcin,Niedziejko, Paulina,Olech, Kamila,Pawlik, Henryk,W?oszczak, ?ukasz,Zuchowicz, Karol,Suarez Alvarez, Jose Ramon,Martyka, Justyna,Sitek, Ewa,Mikulski, Maciej,Szcz??niak, Joanna,J?ckel, Sven,Krier, Mireille,Król, Marcin,Wegener, Ansgar,Ga??zowski, Micha?,Nowak, Mateusz,Becker, Frank,Herhaus, Christian
-
supporting information
p. 11904 - 11933
(2021/09/02)
-
- BODIPY compounds containing 8-(diphenylethynyl)-ester groups as well as synthesis and application thereof
-
The invention discloses BODIPY compounds containing 8-(diphenylethynyl)-ester groups as well as a preparation method and application thereof. The BODIPY compounds have a structure A. According to theinvention, BODIPY is used as a matrix, a diphenylacetylene rigid structure and an ester-based alkyl chain flexible structure are introduced to the No. 8 site through the Sonogashira coupling reaction,and a series of 8-(diphenylethynyl)-ester-based BODIPY dichroic dyes are designed and synthesized. The maximum emission wavelength of the compounds in dichloromethane is concentrated at about 518 nm,green fluorescence is shown, and good dichroic ratio and ordered parameters are shown in a liquid crystal E7; and the liquid crystal compounds provided by the invention have a liquid crystal mesophase within a temperature range of 50-100 DEG C, can be used for manufacturing liquid crystal display products, and particularly can be used as guest body dyes for guest-host mode liquid crystal displays; and when the compounds are added into the E7 liquid crystal and used in a guest-host display mode, response time can be prolonged, and the effect of quick response is achieved.
- -
-
Paragraph 0034; 0042-0044
(2021/02/06)
-
- Field-induced single-ion magnets exhibiting tri-axial anisotropy in a 1D Co(ii) coordination polymer with a rigid ligand 4,4′-(buta-1,3-diyne-1,4-diyl)dibenzoate
-
Herein a 1D Co(ii) coordination polymer of formula [Co(η1-L1)(η2-L1)(py)2(H2O)]n (CoCP) has been synthesised using the rigid H2L1 proligand, containing a long spacer bearing two triple bonds. Single-crystal X-ray diffraction showed that Co(ii) adopts a distorted octahedral geometry. The state-averaged complete active self-consistent field (SA-CASSCF) calculation showed that the ground state of CoCP is a high spin quartet with a highly multiconfigurational character of its electronic structure. Due to the large intra- and intermolecular distances between the spin carriers, the magnetic interactions are negligible and the zero-field splitting (ZFS) effects of cobalt(ii) ions are predominant. This behavior was confirmed by direct current (DC) magnetic measurements and theoretical calculations using the broken-symmetry approach. Quantum chemical calculations indicate that CoCP has a negative axial component possessing mixed tri-axial anisotropy. The DC magnetic susceptibility data were fitted with a Griffith-Figgis Hamiltonian and the obtained parameters are in good agreement with those simulated by the ab initio calculation. Alternating current (AC) magnetic measurements showed a field induced slow magnetic relaxation in CoCP, which is attributed to the hyperfine interaction effects.
- C. Silva, Henrique,Ferreira, Glaucio B.,Guedes, Guilherme P.,Matos, Catiúcia R. M. O.,Nunes, Wallace C.,Ronconi, Célia M.,Sarmiento, Charlie V.
-
p. 15003 - 15014
(2021/11/17)
-
- Design, synthesis and antitumor evaluations of nucleoside base hydroxamic acid derivatives as DNMT and HDAC dual inhibitors
-
DNA methyltransferase (DNMT) and histone deacetylase (HDAC) are well recognized epigenetic targets for discovery of antitumor agents. In this study, we designed and synthesized a series of nucleoside base hydroxamic acid derivatives as DNMT and HDAC dual inhibitors. MTT assays and enzymatic inhibitory activity tests indicated that compound 204 exhibited potent DNMT1 and HDAC1/6 inhibitory potency simultaneously in enzymatic levels and at cellular levels, inducing hypomethylation of p16 and hyperacetylation of histones H3K9 and H4K8. Besides, 204 remarkably inhibited proliferation against cancer cells U937 by prompting G0/G1 cell cycle arrest. Molecular docking models explained the functional mechanism of 204 inhibiting DNMT1 and HDAC. Preliminary studies on metabolic profiles revealed that 204 showed desirable stability in liver microsomes. Our study suggested that 204 inhibiting DNMT and HDAC concurrently can be a potential lead compound for epigenetic cancer therapy.
- Sun, Qinsheng,Dai, Qiuzi,Zhang, Cunlong,Chen, Yan,Zhao, Lei,Yuan, Zigao,Jiang, Yuyang
-
supporting information
p. 2479 - 2483
(2021/03/08)
-
- One-step Ethylene Purification from an Acetylene/Ethylene/Ethane Ternary Mixture by Cyclopentadiene Cobalt-Functionalized Metal–Organic Frameworks
-
The separation of ethylene (C2H4) from a mixture of ethane (C2H6), ethylene (C2H4), and acetylene (C2H2) at normal temperature and pressure is a significant challenge. The sieving effect of pores is powerless due to the similar molecular size and kinetic diameter of these molecules. We report a new modification method based on a stable ftw topological Zr-MOF platform (MOF-525). Introduction of a cyclopentadiene cobalt functional group led to new ftw-type MOFs materials (UPC-612 and UPC-613), which increase the host-guest interaction and achieve efficient ethylene purification from the mixture of hydrocarbon gases. The high performance of UPC-612 and UPC-613 for C2H2/C2H4/C2H6 separation has been verified by gas sorption isotherms, density functional theory (DFT), and experimentally determined breakthrough curves. This work provides a one-step separation of the ternary gas mixture and can further serve as a blueprint for the design and construction of function-oriented porous structures for such applications.
- Wang, Yutong,Hao, Chunlian,Fan, Weidong,Fu, Mingyue,Wang, Xiaokang,Wang, Zhikun,Zhu, Lei,Li, Yue,Lu, Xiaoqing,Dai, Fangna,Kang, Zixi,Wang, Rongming,Guo, Wenyue,Hu, Songqing,Sun, Daofeng
-
supporting information
p. 11350 - 11358
(2021/04/05)
-
- COMPOUND ACTING AS ANTIBIOTICS
-
The present invention provides a novel antibiotic compound represented by the following formula (I), a pharmaceutically acceptable salt thereof, an ester thereof, a prodrug thereof, a solvate thereof, or a deuterated analog thereof, or a stereoisomer thereof. The compound of the present invention exhibits excellent antibacterial activity, especially against Gram bacteria. wherein each group is defined as in the description.
- -
-
Paragraph 0195; 0204-0205; 0307; 0310-0311
(2020/12/22)
-
- Development of helical aromatic amide foldamers with a diphenylacetylene backbone
-
We designed and synthesized aromatic polyamides with a diphenylacetylene backbone, α-DPA and β-DPA, bearing (S)-α-and (S)-β-methyl-substituted triethyleneglycol (TEG) side chains, respectively, and examined their conformations in solution. Both polymers exhibit strong, solvent polarity-dependent circular dichroism spectra, which indicated that they take helical conformations in low-polarity solvents. The spectra were mirror images, depending on the chiral position of the side chains. Thus, the polyamide α-DPA bearing (S)-α-methyl-substituted TEG groups takes a left-handed helical conformation, while the polyamide β-DPA with (S)-β-methyl-substituted TEG groups takes a right-handed helical conformation. The difference in the screw sense of α-DPA and β-DPA would be caused by the steric interaction between the main chain and the side chain, as observed in poly(p-benzamide) possessing (S)-β-methyl-substituted TEG side chains (β-PA) because the large cavity of the helical structure of DPA would disturb the solvophobically induced helical folding. Detailed conformational analyses of the oligoamides 6-12 with β-methyl-substituted TEG groups were conducted. Theoretical calculations indicated that the oligoamides with β-methyl-substituted TEG groups exist in a helical conformation with a cavity of 7 ? in diameter. The 1H NMR spectra of the oligomers revealed interactions with small anions such as chloride and acetate anions and with pyridinium cations.
- Azumaya, Isao,Kagechika, Hiroyuki,Masu, Hyuma,Mori, Hirotoshi,Tanatani, Aya,Urushibara, Ko,Yamada, Tatsunori,Yokoyama, Akihiro,Yokozawa, Tsutomu
-
p. 2019 - 2039
(2020/03/13)
-
- Solvent Adaptive Dynamic Metal-Organic Soft Hybrid for Imaging and Biological Delivery
-
A solvent responsive dynamic nanoscale metal-organic framework (NMOF) [Zn(1 a)(H2O)2] has been devised based on the self-assembly of ZnII and asymmetric bola-amphiphilic oligo-(p-phenyleneethynylene) (OPE) dicarboxylate linker 1 a having dodecyl and triethyleneglycolmonomethylether (TEG, polar) side chains. In THF solvent, NMOF showed nanovesicular morphology (NMOF-1) with surface decorated dodecyl chains. In water and methanol, NMOF exhibited inverse-nanovesicle (NMOF-2) and nanoscroll (NMOF-3) morphology, respectively, with surface projected TEG chains. The pre-formed NMOFs also unveiled reversible solvent responsive transformation of different morphologies. The flexible NMOF showed cyan emission and no cytotoxicity, allowing live cell imaging. Cisplatin (14.4 wt %) and doxorubicin (4.1 wt %) were encapsulated in NMOF-1 by non-covalent interactions and, in vitro and in vivo drug release was studied. The drug loaded NMOFs exhibited micromolar cytotoxicity.
- Samanta, Debabrata,Roy, Syamantak,Sasmal, Ranjan,Saha, Nilanjana Das,Pradeep,Viswanatha, Ranjani,Agasti, Sarit S.,Maji, Tapas Kumar
-
supporting information
p. 5008 - 5012
(2019/03/11)
-
- Pure white light emission and charge transfer in organogels of symmetrical and unsymmetrical π-chromophoric oligo-: P -(phenyleneethynylene) bola-amphiphiles
-
Two novel bola-amphiphilic oligo-p-(phenyleneethynylene) (OPE) dicarboxylates have been synthesized having non-polar and mixed-polar side chains. This led to gelation in both with vesicular morphology. Upon in situ loading of a suitable dye and redox-active molecule, pure white light emitting and charge transfer (CT)-gels, respectively, were realized.
- Roy, Syamantak,Samanta, Debabrata,Kumar, Pramod,Maji, Tapas Kumar
-
supporting information
p. 275 - 278
(2018/01/12)
-
- Design, synthesis and structure-activity relationship evaluation of novel LpxC inhibitors as Gram-negative antibacterial agents
-
LpxC inhibitors are new-type antibacterial agents developed in the last twenty years, mainly against Gram-negative bacteria infections. To develop novel LpxC inhibitors with good antibacterial activities and biological metabolism, we summarized the basic skeleton of reported LpxC inhibitors, designed and synthesized several series of compounds and tested their antibacterial activities against Escherichial coli and Pseudomonas aeruginosa in vitro. Structure-activity relationships have been discussed in this article. The metabolism stability of YDL-2, YDL-5, YDL-8, YDL-14, YDL-20–YDL-23 have been evaluated in liver microsomes, which indicated that the 2-amino isopropyl group may be a preferred structure than the 2-hydroxy ethyl group in the design of LpxC inhibitors.
- Ding, Shi,Dai, Rui-Yang,Wang, Wen-Ke,Cao, Qiao,Lan, Le-Fu,Zhou, Xian-Li,Yang, Yu-She
-
supporting information
p. 94 - 102
(2017/12/15)
-
- Metal-free synthesis of imidazole by BF3·Et2O promoted denitrogenative transannulation of N-sulfonyl-1,2,3-triazole
-
BF3·Et2O promoted metal-free denitrogenative transannulation of N-sulfonyl-1,2,3-triazole was reported. Rather than transition metals, BF3·Et2O was employed for the first time to promote the formation of α-diazoimines from N-sulfonyl-1,2,3-triazoles in nitriles, leading to the synthesis of various imidazoles. The protocol tolerates a broad range of functional groups and could also be applied to the late-stage modification of bioactive molecules, demonstrating the potential of this protocol in organic synthesis. A plausible mechanism was proposed.
- Yang, Dongdong,Shan, Lihong,Xu, Ze-Feng,Li, Chuan-Ying
-
supporting information
p. 1461 - 1464
(2018/03/08)
-
- Solvent-Modulated Emission Properties in a Superhydrophobic Oligo(p-phenyleneethynylene)-Based 3D Porous Supramolecular Framework
-
A chromophoric oligo(p-phenyleneethynylene) (OPE) bola-amphiphile with dioxyoctyl side chains (H2OPE-C8) has been self-assembled with CdII to form a 1D coordination polymer, {Cd(OPE-C8)(DMF)2(H2O)} (1), which is further interdigitated to form a 2D network. Such 2D networks are further interwoven to form a 3D supramolecular framework with surface-projected alkyl chains. The desolvated framework showed permanent porosity, as realized from the CO2 adsorption profile. 1 showed high water contact angles, portraying its superhydrophobic nature. 1 also showed a linker-based cyan luminescence. Solvent removal led to a bathochromic shift in emission into the green region. Resolvation with N,N-dimethylformamide brought back the original cyan emission, whereas for tetrahydrofuran, ethanol, and methanol, it persisted at an intermediate state. Density functional theory calculations unraveled that, twisting of the OPE phenyl rings generated the red shift in emission.
- Roy, Syamantak,Suresh, Venkata M.,Hazra, Arpan,Bandyopadhyay, Arkamita,Laha, Subhajit,Pati, Swapan. K.,Maji, Tapas Kumar
-
supporting information
p. 8693 - 8696
(2018/08/17)
-
- An Amino-Functionalized Metal-Organic Framework, Based on a Rare Ba12(COO)18(NO3)2 Cluster, for Efficient C3/C2/C1 Separation and Preferential Catalytic Performance
-
A barium(II) metal-organic framework (MOF) based on a predesigned amino-functionalized ligand, namely [Ba2(L)(DMF)(H2O)(NO3)1/3]?DMF?EtOH?2 H2O (UPC-33) [H3L=4,4′-((2-amino-5-carboxy-1,3-phenylene)bis(ethyne-2,1-diyl))dibenzoic acid] has been synthesized. UPC-33 is a 3-dimensional 3,18-connected network with fcu topology with a rare twelve-nuclear Ba12(COO)18(NO3)2 cluster. UPC-33 shows permanent porosity and a high adsorption heat of CO2 (49.92 kJ mol?1), which can be used as a platform for selective adsorption of CO2/CH4 (8.09). In addition, UPC-33 exhibits high separation selectivity for C3 light hydrocarbons with respect to CH4 (228.34, 151.40 for C3H6/CH4, C3H8/CH4 at 273k and 1 bar), as shown by single component gas sorption and selectivity calculations. Due to the existence of ?NH2 groups in the channels, UPC-33 can effectively catalyze Knoevenagel condensation reactions with high yield, and substrate size and electron dependency.
- Fan, Weidong,Wang, Yutong,Zhang, Qian,Kirchon, Angelo,Xiao, Zhenyu,Zhang, Liangliang,Dai, Fangna,Wang, Rongming,Sun, Daofeng
-
supporting information
p. 2137 - 2143
(2017/12/13)
-
- Expanding the group of Porous Interpenetrated Zr-Organic Frameworks (PIZOFs) with linkers of different lengths
-
A Zr-based MOF of the PIZOF type, which consists of two independent and mutually interpenetrating UiO-type frameworks with [Zr6O4(OH)4(O2C)12] nodes, does not only form with a PEPEP dicarboxylic acid (P = phenylene, E = ethynylene). Also dicarboxylic acids with the shorter PPPP and PEPP spacers were found to give PIZOFs, denoted PPPP-PIZOF and PEPP-PIZOF, respectively. Reducing the spacer length even further to a PEEP segment caused a switchover to the formation of a UiO framework. The hysteresis in the Ar sorption curve of PEPP-PIZOF-1 and the slightly too large amount of combustion residue from PPPPPIZOF- 1 suggest structural defects. These hint at a mismatch between the requirement of the optimal linker length for PIZOF formation and the lengths of the PEPP and PPPP dicarboxylates. Nevertheless, these dicarboxylates prefer the formation of a PIZOF over the formation of a UiO structure. PEPEP-PIZOF-2, PPPP-PIZOF-1, and PEPP-PIZOF-1 are stable in air up to 325, 350, and 300 °C, respectively, and have BET surface areas of 2350, 2020, and 1650 m2 g-1, respectively. PEPEP-PIZOFs, even those with very hydrophilic oligo(ethylene glycol) side chains on the linkers, are very stable in water and also during drying from a water-wetted state. On the contrary, PEPP-PIZOF-1 and PPPP-PIZOF-1 that had been exposed to water required exchange of water for ethanol before drying to mostly preserve the framework. The results emphasize the importance of differentiating between framework damage caused through hydrolysis in water and through drying from a water-wetted state. The sensitivity of PEPP-PIZOF-1 and PPPP-PIZOF-1 against drying from a water-wetted state may be the consequence of defects. The drying stability of water-wetted PEPEP-PIZOFs lets us suggest that reversible bending of the linkers contributes to the stability of the PEPEP-PIZOFs.
- Lippke, Jann,Brosent, Birte,Von Zons, Tobias,Virmani, Erika,Lilienthal, Sebastian,Preu?e, Thomas,Hulsmann, Miriam,Schneider, Andreas M.,Wuttke, Stefan,Behrens, Peter,Godt, Adelheid
-
p. 748 - 761
(2017/01/25)
-
- Bacteriochlorin-based organic dye
-
Disclosed herein is a bacteriochlorin-based organic dye represented by Formula (II): wherein the substituents contained in Formula (II) are as defined herein. The bacteriochlorin-based organic dye is stable in air, and may be used as a photosensitizer in dye-sensitized solar cell.
- -
-
Page/Page column 32; 35; 36
(2017/08/01)
-
- Substituent Effects That Control Conjugated Oligomer Conformation through Non-covalent Interactions
-
Although understanding the conformations and arrangements of conjugated materials as solids is key to their prospective applications, predictive power over these structural factors remains elusive. In this work, substituent effects tune non-covalent interactions between side-chain fluorinated benzyl esters and main-chain terminal arenes, in turn controlling the conformations and interchromophore aggregation of three-ring phenylene-ethynylenes (PEs). Cofacial fluoroarene-arene (ArF-ArH) interactions cause twisting in the PE backbone, interrupting intramolecular conjugation as well as blocking chromophore aggregation, both of which prevent the typically observed bathochromic shift observed upon transitioning PEs from solution to solid. This work highlights two structural factors that determine whether the ArF-ArH interactions, and the resulting twisted, unaggregated chromophores, occur in these solids: (i) the electron-releasing characteristic of substituents on ArH, with more electron-releasing character favoring ArF-ArH interactions, and (ii) the fluorination pattern of the ArF ring, with 2,3,4,5,6-pentafluorophenyl favoring ArF-ArH interactions over 2,4,6-trifluorophenyl. These trends indicate that considerations of electrostatic complementarity, whether through a polar-π or substituent-substituent mechanism, can serve as an effective design principle in controlling the interaction strengths, and therefore the optoelectronic properties, of these molecules as solids.
- Sharber, Seth A.,Baral, Rom Nath,Frausto, Fanny,Haas, Terry E.,Müller, Peter,Thomas, Samuel W.
-
supporting information
p. 5164 - 5174
(2017/05/04)
-
- Photochemical Dual-Catalytic Synthesis of Alkynyl Sulfides
-
A photochemical dual-catalytic cross-coupling to form alkynyl sulfides via C(sp)?S bond formation is described. The cross-coupling of thiols and bromoalkynes is promoted by a soluble organic carbazole-based photocatalyst using continuous flow techniques. Synthesis of alkynyl sulfides bearing a wide range of electronically and sterically diverse aromatic alkynes and thiols can be achieved in good to excellent yields (50–96 %). The simple continuous flow setup also allows for short reaction times (30 min) and high reproducibility on gram scale. In addition, we report the first application of photoredox/nickel dual catalysis towards macrocyclization, as well as the first example of the incorporation of an alkynyl sulfide functional group into a macrocyclic scaffold.
- Santandrea, Jeffrey,Minozzi, Clémentine,Cruché, Corentin,Collins, Shawn K.
-
supporting information
p. 12255 - 12259
(2017/09/06)
-
- Light induced construction of porous covalent organic polymeric networks for significant enhancement of CO2 gas sorption
-
Herein, we report morphology-controlled porous polymeric materials for enhanced CO2 capture, which was achieved using the topochemical polymerization of dipeptide functionalized diphenylbutadiynes. The topochemical reaction was executed to control the morphology of the synthesized dipeptide appended diarylbutadiyne derivatives on a solid surface. Topochemical polymerization involves the formation of polydiacetylene due to the presence of hydrogen bonding between the amide groups and intermolecular π-π stacking interactions in their self-assembled state, which was established using UV-Vis, Raman and IR spectroscopy. The change in morphology of the two dipeptide functionalized diphenylbutadiyne (DPB) was confirmed by scanning electron microscopy. Porosity was developed after UV irradiation of the diacetylene-based dipeptide appended bolaamphiphiles. Interestingly, after UV irradiation, the porous covalent organic polymers 1 and 2 show 24.22 times and 12 times enhanced N2 gas adsorption than their parent compounds 1 and 2, respectively. The surface area of the porous covalent organic polymers 1 and 2 was enhanced 21.68 times and 5.54 times than their parent compounds 1 and 2, respectively. Polymer 1 exhibits 4.23 times the CO2 capture ability than compound 1 and polymer 2 shows 4.1 times the CO2 capture ability than compound 2. This study highlights the controlled synthesis of light induced porous covalent organic polymers with high surface area used for efficient CO2 storage applications.
- Bhowmik, Soumitra,Konda, Maruthi,Das, Apurba K.
-
p. 47695 - 47703
(2017/10/19)
-
- Unusual C-I?O halogen bonding in triazole derivatives: Gelation solvents at two extremes of polarity and formation of superorganogels
-
To investigate the influence of halogen bond (XB) on the gelation of a one-component organogel system, a new family of 5-iodo-1H-1,2,3-triazole and 1H-1,2,3-triazole gelators was designed and synthesized. The iodo gelators (1I, 3I) gelled various solvents at low concentrations and formed many superorganogels, whereas the hydrogenous gelators (1H, 3H) showed much poorer gelling performance. An X-ray analysis of the single crystals of two reference compounds (16I, 16H) reveals that the unusual C-I?O XB interaction is responsible for this difference. The results of spectroscopic examinations (XRD, SEM, 1H NMR, and UV) are well consistent with those of single-crystal analyses. Under the guidance of the XB interaction and the weak π-π interaction, 1I and 3I self-assemble to hexagonal columnar aggregations in the gel state, whereas 1H and 3H, driven by CH-π interactions, feature the formation of gels with a lamellar structure. The mechanical property of iodo gels is much better than that of hydrogenous gels under the same concentration. Gels from 1I respond to the stimuli of Hg2+, Cu2+, Zn2+, and Mg2+ as perchlorate salts, and gels from 1H are selectively responsive to Hg2+ solely.
- Huang, Yaodong,Li, Huimin,Li, Ziyan,Zhang, Yan,Cao, Wenwen,Wang, Luyuan,Liu, Shuxue
-
p. 311 - 321
(2017/03/29)
-
- Direct spirocyclization from keto-sulfonamides: An approach to azaspiro compounds
-
Spontaneous spirocyclization of keto-sulfonamides via ynamides through a one-pot process is presented. Push-pull ynamides were obtained through Michael addition/elimination without Cu. The obtained azaspiro compounds are building blocks for indole alkaloids. Theoretical studies provide insights into the mechanism of the formal Conia-ene reaction.
- Beltran, Frédéric,Fabre, Indira,Ciofini, Ilaria,Miesch, Laurence
-
supporting information
p. 5042 - 5045
(2017/11/06)
-
- Copper(I)-catalyzed stereoselective hydrogenation of 1,3-diynes and enynes
-
A stereoselective hydrogenation of 1,3-diynes with an air-stable copper(I)/N-heterocyclic carbene complex, [IPrCuOH], has been developed. The corresponding products, 1,3-dienes, are obtained in a stereoselective manner depending on their substitution pattern: Diaryl-diynes yield E,E-1,3-dienes, whereas dialkyl-diynes are converted to the corresponding Z,Z-1,3-dienes. Hydrogenation and deuteration experiments with enynes indicate that these are competent reaction intermediates in the hydrogenation of diynes.
- Thiel, Niklas O.,Kemper, Sebastian,Teichert, Johannes F.
-
p. 5023 - 5028
(2017/07/27)
-
- Nucleoside and base hydroxamic acid derived compound and preparation method and applications thereof
-
The invention discloses a nucleoside and base hydroxamic acid compound with DNA transmethylase and/or histone deacetylase inhibition activity, and a preparation method and applications thereof. The structural formula of the nucleoside and base hydroxamic acid compound is shown as the formula I, wherein R is nucleoside and base, nucleoside and base with substituent group or nucleoside and base analogue in DNA and/or RNA; Linker is a connecting chain connecting R with hydroxamic acid function group, the connecting chain comprises but is not limited within alkyl chain, alkyl chain with heteroatom, alkyl chain with aromatic ring, and alkyl chain with heterocycle. In-vitro cell proliferation assay show that the compound shown in the formula I can well inhibit the proliferation of leukemia cell K562 and histocyte lymphoma cell U937. Transmethylase and histone deacetylase inhibition assay shows that the compound shown in the formula I is a compound having inhibition activity on the DNA transmethylase and/or histone deacetylase. The formula I is as shown in the specification.
- -
-
Paragraph 0185
(2017/08/29)
-
- Synthesis and properties of bis-porphyrin molecular tweezers: Effects of spacer flexibility on binding and supramolecular chirogenesis
-
Ditopic binding of various dinitrogen compounds to three bisporphyrin molecular tweezers with spacers of varying conformational rigidity, incorporating the planar enediyne (1), the helical stiff stilbene (2), or the semi-rigid glycoluril motif fused to the porphyrins (3), are compared. Binding constants Ka = 104-106 M-1 reveal subtle differences between these tweezers, that are discussed in terms of porphyrin dislocation modes. Exciton coupled circular dichroism (ECCD) of complexes with chiral dinitrogen guests provides experimental evidence for the conformational properties of the tweezers. The results are further supported and rationalized by conformational analysis.
- Blom, Magnus,Norrehed, Sara,Andersson, Claes-Henrik,Huang, Hao,Light, Mark E.,Bergquist, Jonas,Grennberg, Helena,Gogoll, Adolf
-
supporting information
(2016/02/05)
-
- Stereoselective Halogenation of Integral Unsaturated C-C Bonds in Chemically and Mechanically Robust Zr and Hf MOFs
-
Metal-organic frameworks (MOFs) containing ZrIV-based secondary building units (SBUs), as in the UiO-66 series, are receiving widespread research interest due to their enhanced chemical and mechanical stabilities. We report the synthesis and extensive characterisation, as both bulk microcrystalline and single crystal forms, of extended UiO-66 (Zr and Hf) series MOFs containing integral unsaturated alkene, alkyne and butadiyne units, which serve as reactive sites for postsynthetic modification (PSM) by halogenation. The water stability of a Zr-stilbene MOF allows the dual insertion of both -OH and -Br groups in a single, aqueous bromohydrination step. Quantitative bromination of alkyne- A nd butadiyne-containing MOFs is demonstrated to be stereoselective, as a consequence of the linker geometry when bound in the MOFs, while the inherent change in hybridisation and geometry of integral linker atoms is facilitated by the high mechanical stabilities of the MOFs, allowing bromination to be characterised in a single-crystal to single-crystal (SCSC) manner. The facile addition of bromine across the unsaturated C-C bonds in the MOFs in solution is extended to irreversible iodine sequestration in the vapour phase. A large-pore interpenetrated Zr MOF demonstrates an I2 storage capacity of 279 % w/w, through a combination of chemisorption and physisorption, which is comparable to the highest reported capacities of benchmark iodine storage materials for radioactive I2 sequestration. We expect this facile PSM process to not only allow trapping of toxic vapours, but also modulate the mechanical properties of the MOFs.
- Marshall, Ross J.,Griffin, Sarah L.,Wilson, Claire,Forgan, Ross S.
-
supporting information
p. 4870 - 4877
(2016/04/05)
-
- Transition-metal-free regioselective synthesis of alkylboronates from arylacetylenes and vinyl arenes
-
A transition-metal-free synthesis of alkylboronates, utilizing arylacetylenes or vinyl arenes and bis(pinacolato)diboron through tandem borylation and protodeboronation, has been developed. This reaction is efficient, practical and environmentally benign, leading to anti-Markovnikov products with excellent regioselectivity, broad functional group tolerance and excellent yields in both small and gram scales.
- Yang, Kai,Song, Qiuling
-
supporting information
p. 932 - 936
(2016/02/27)
-
- FLUORESCENT SYNTHETIC RETINOIDS
-
There are described novel compounds of formula I: which R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are each as herein defined.
- -
-
Page/Page column 42
(2016/05/02)
-
- Cleavage of the Carbon–Carbon Triple Bonds of Arylacetylenes for the Synthesis of Arylnitriles without a Metal Catalyst
-
Cleavage of the carbon–carbon triple bonds of alkynes was achieved, which led to the synthesis of arylnitriles under transition-metal-free conditions. A vast range of terminal alkyne substrates underwent this reaction to provide the corresponding nitriles in moderate to good yields with good functional group tolerance.
- Lin, Yuanguang,Song, Qiuling
-
supporting information
p. 3056 - 3059
(2016/07/12)
-
- Influence of ethynyl position on benzothiadiazole based D-A-π-A dye-sensitized solar cells: Spectral response and photovoltage performance
-
The ethynyl group has been widely employed in dye-sensitized solar cells (DSSCs) as an efficient π-spacer to prolong conjugation and promote electronic coupling at the interface of TiO2 films. However, systematic studies of the ethynyl position on metal-free organic sensitizers remain relatively rare. Herein we report indoline-based organic dyes bearing an ethynyl group at different positions of D-A-π-A organic dyes. Based on the reference dye D1, we inserted an ethynyl unit in either the left or right side of benzothiadiazole to construct two novel dyes D2 and D3. It was found that inserting an ethynyl unit to the side of the anchoring group obtained a higher molar extinction coefficient with a red shift in the absorption band. Interestingly, D2 and D3 displayed a better photovoltaic performance with respect to D1. In particular, D3 exhibits an over 90 mV enhanced open-circuit voltage (VOC) than D2 owing to a longer electron lifetime and slower charge recombination. With this incredible increase of VOC, D3 bestows a high efficiency of 7.13% with respect to D1 and D2. Coadsorption strategies are exploited for further improving the cell behaviour. As a result, cosensitization with a long-wavelength-responsive dye WS-2 was demonstrated to efficiently compensate the light-harvesting, achieving an excellent efficiency of 9.83% in the iodine electrolyte. This work has paved a useful and practical way for molecular engineering in D-A-π-A metal-free organic dyes.
- Song, Xiongrong,Zhang, Weiwei,Li, Xin,Jiang, Huiyun,Shen, Chao,Zhu, Wei-Hong
-
p. 9203 - 9211
(2016/10/21)
-
- Synthesis of 1-arylsulfonyl-1,2,3-triazoles from (Z)-arylvinyl bromides by sequential elimination–cycloaddition reaction
-
[Figure not available: see fulltext.]Efficient synthesis of 1-arylsulfonyl-1,2,3-triazoles from easily available (Z)-arylvinyl bromides is described. The sequential reaction involves elimination of HBr from (Z)-arylvinyl bromides promoted by KOH and copper-catalyzed (3+2) cycloaddition reaction between the alkyne intermediates and sulfonyl azides.
- Zhang, Wensheng,Xu, Wenjing
-
p. 192 - 195
(2016/07/28)
-
- Synthesis and biological evaluation of a novel betulinic acid derivative as an inducer of apoptosis in human colon carcinoma cells (HT-29)
-
Abstract A novel family of betulinic acid analogues, carrying a triazole unit at C-3 attached through a linker, was synthesized by the application of azide-alkyne "Click reaction". These were screened for their anticancer activity against different cancer cells and normal human PBMC by MTT assay. Compound 2c [(3S)-3-{2-(4-(hydroxymethyl-1H-1,2,3-triazol-1-yl)acetyloxy}-lup-20(29)-en-28-oic acid] was found as the most potent inhibitor of cell line HT-29 with IC50 value 14.9 μM. Its role as an inducer of apoptosis was investigated in this cell line by Annexin-V/PI binding assay and by following its capability for ROS generation, depolarization of mitochondrial transmembrane potential, activation of caspases, PARP cleavage, nuclear degradation and expression of pro- and anti-apoptotic proteins. It exhibited much higher cytotoxicity than the standard drug 5-fluorouracil but showed negligible cytotoxicity towards normal PBMC. Elevated level of ROS generation, activation of caspase 3 and caspase 9, DNA fragmentation, higher expression of Bax and Bad, lower expression of Bcl2 and Bcl-xl, and increased level of Bax/Bcl-xl ratio identified 2c as a promising inducer of apoptosis that follows a mitochondria dependent pathway. Bio-physical studies indicate that compound 2c acts as a minor groove binder to the DNA.
- Chakraborty, Biswajit,Dutta, Debasmita,Mukherjee, Sanjukta,Das, Supriya,Maiti, Nakul C.,Das, Padma,Chowdhury, Chinmay
-
supporting information
p. 93 - 105
(2015/08/18)
-
- Differential Targeting of Human Topoisomerase II Isoforms with Small Molecules
-
(Chemical Equation Presented). The TOP2 poison etoposide has been implicated in the generation of secondary malignancies during cancer treatment. Structural similarities between TOP2 isoforms challenge the rational design of isoform-specific poisons to further delineate these processes. Herein, we describe the synthesis and biological evaluation of a focused library of etoposide analogues, with the identification of two novel small molecules exhibiting TOP2B-dependent toxicity. Our findings pave the way toward studying isoform-specific cellular processes by means of small molecule intervention.
- Mariani, Angelica,Bartoli, Alexandra,Atwal, Mandeep,Lee, Ka C.,Austin, Caroline A.,Rodriguez, Rapha?l
-
supporting information
p. 4851 - 4856
(2015/06/25)
-
- RAFAMYCIN ANALOGS AND METHODS FOR MAKING SAME
-
A semi-synthetic rapamycin analog with a triazole moiety or a pharmaceutically acceptable salt or prodrug thereof, is a broad-spectrum cytostatic agent and a mTOR inhibitor, and is useful in the treatment of various cancers, or tumors in organs such as kidney, liver, breast, head and neck, lung, prostate, and restenosis in coronary arteries, peripheral arteries, and arteries in the brain, immune and autoimmune diseases. Also disclosed are fungal growth-, restenosis-, post-transplant tissue rejection- and immune- and autoimmune disease-inhibiting compositions and a method of inhibiting cancer, fungal growth, restenosois, post-transplant tissue rejection, and immune and autoimmune disease in a mammal. One particular preferred application of such triazole-moiety containing rapamycin analog is in treating renal carcinoma, lung cancer, colon cancer, and breast cancers wherein potency of the drug, its half-life, tissue distribution properties, and its pharmacokinetic properties including bioavailability through oral and intravenous routes are essential to the clinical outcomes.
- -
-
Paragraph 0111
(2015/02/25)
-
- Visible-Light-Promoted Vinylation of Tetrahydrofuran with Alkynes through Direct C-H Bond Functionalization
-
(Chemical Equation Presented) Mild and direct C-H bond functionalizations and vinylations of tetrahydrofuran with alkynes have been accomplished through visible light photocatalysis, yielding a range of vinyl tetrahydrofurans under the synergistic actions of organic dye-type photocatalyst eosin Y, tert-butyl hydroperoxide (t-BuOOH), and a 45 W household lightbulb. A significant kinetic isotope effect (KIE) was recorded, which helps shed light on the mechanistic course.
- Li, Jing,Zhang, Jing,Tan, Haibo,Wang, David Zhigang
-
supporting information
p. 2522 - 2525
(2015/05/27)
-
- ANTIBACTERIAL AGENTS
-
Antibacterial compounds of formula (I) are provided, as well as stereoisomers and pharmaceutically acceptable salts and esters thereof; pharmaceutical compositions comprising such compounds; methods of treating bacterial infections by the administration of such compounds; and processes for the preparation of such compounds.
- -
-
Page/Page column 41
(2014/10/18)
-
- Combined spectroscopic and quantum chemical study of [trans-Ru(C≡CC6H4R1-4)2(dppe)2]n+ and [trans-Ru(C≡CC6H4R1-4)(C≡CC6H4R2-4)(dppe)2]n+ (n = 0, 1) complexes: Interpretations beyond the lowest energy conformer paradigm
-
The reaction of trans-RuCl(C≡CC6H4R1-4)(dppe)2 (2: R1 = Me (a), C5H11 (b), OMe (c), CO2Me (d), NO2 (e), C≡CSiMe3 (f), C≡CBut (g), NH2 (h)), prepared in situ from reactions of [RuCl(dppe)2]OTf ([1]OTf) with terminal alkynes in CH2Cl2 solutions containing 1,8-diazabicycloundec-7-ene (DBU) and TlBF4, provides a convenient and rapid route to bis(acetylide) complexes trans-Ru(C≡CC6H4R1-4)2(dppe)2 (3a-h) and trans-Ru(C≡ CC6H4R1-4)(C≡CC6H4R2-4)(dppe)2 (4, R1 = C≡CSiMe3, R2 = NH2; 5, R1 = CO2Me, R2 = NH2; 6, R1 = CO2Me, R2 = OMe). However, even in the absence of the chloride abstracting reagent, more strongly electron donating substituents (e.g., R1 = OMe (2c), NH2 (2h)) promote sufficient ionization of the Ru-Cl bond in trans-RuCl(C≡CC6H4R -4)(dppe)2 to lead to slow conversion to bis(alkynyl) complexes 3c,h in the presence of excess alkyne and DBU. Desilylation of 2f and 3f affords 2i and 3i (R1 = C≡CH), respectively. The molecular structures of 3a-d,f-i have been determined and are reported together with the structures of the monoalkynyl complexes 2f,g,i and compared with related compounds from the literature. Complexes 3a-i and 4-6 undergo one reversible electrochemical oxidation process, which can be attributed to depopulation of an orbital with significant alkynyl ligand character. The one-electron-oxidation products [3f]?+, [3h]?+, [4]?+, and [5]?+, chosen to serve as representative examples of this family of complexes, each exhibit a series of NIR absorptions between 15000 and 5000 cm-1 which on the basis of TDDFT calculations cannot be attributed to a single, static lowest energy molecular structure. Rather, the transitions that are responsible for the absorption band envelope have varying degrees of LMCT and inter-alkynyl ligand IVCT or MLCT character that depend not only on the nature of the Rn groups but also on the ensemble of thermally populated molecular conformers in solution with various relative orientations of the metal fragment and arylethynyl moieties. (Figure Presented)
- Marqués-González, Santiago,Parthey, Matthias,Yufit, Dmitry S.,Howard, Judith A.K.,Kaupp, Martin,Low, Paul J.
-
supporting information
p. 4947 - 4963
(2015/04/27)
-
- IAP ANTAGONISTS
-
There are disclosed compounds that modulate the activity of inhibitors of apoptosis (lAPs), pharmaceutical compositions containing said compounds and methods of treating proliferative disorders and disorders of dysregulated apoptosis, such as cancer, utilizing the compounds of the invention.
- -
-
Paragraph 00133; 00179
(2014/02/15)
-
- Autotandem catalysis: Synthesis of pyrroles by gold-catalyzed cascade reaction
-
A novel synthesis of substituted pyrroles by a gold(I)-catalyzed cascade reaction has been developed. The reaction proceeded with an autotandem catalysis consisting of an initial addition of gold-acetylide to an acetal moiety and was followed by gold-catalyzed 5-endo-dig cyclization and aromatization. Gold catalysts play a dual role in activating nucleophilicity or electrophilicity of terminal acetylenes by forming gold-acetylides or by π-coordination. The formal (3 + 2) annulation of two components provided a variety of substituted pyrroles in a modular fashion.
- Ueda, Hirofumi,Yamaguchi, Minami,Kameya, Hiroshi,Sugimoto, Kenji,Tokuyama, Hidetoshi
-
supporting information
p. 4948 - 4951
(2015/04/27)
-
- RAFAMYCIN ANALOGS AND METHODS FOR MAKING SAME
-
A semi-synthetic rapamycin analog with a triazole moiety or a pharmaceutically acceptable salt or prodrug thereof, is a broad-spectrum cytostatic agent and a m TOR inhibitor, and is useful in the treatment of various cancers, or tumors in organs such as kidney, liver, breast, head and neck, lung, prostate, and restenosis in coronary arteries, peripheral arteries, and arteries in the brain, immune and autoimmune diseases. Also disclosed are fungal growth-, restenosis-, post- transplant tissue rejection- and immune- and autoimmune disease- inhibiting compositions and a method of inhibiting cancer, fungal growth, restenosois, post-transplant tissue rejection, and immune and autoimmune disease in a mammal. One particular preferred application of such triazole-moiety containing rapamycin analog is in treating renal carcinoma, lung cancer, colon cancer, and breast cancers wherein potency of the drug, its half-life, tissue distribution properties, and its pharmacokinetic properties including bioavailability through oral and intravenous routes are essential to the clinical outcomes.
- -
-
Paragraph 66
(2014/06/23)
-
- Mechanochromic behavior of aryl-substituted buta-1,3-diene derivatives with aggregation enhanced emission
-
Three tetra-aryl substituted 1,3-butadiene derivatives with aggregation enhanced emission (AEE) and mechanochromic fluorescence behavior have been rationally designed and synthesized. The results suggest an effective design strategy for developing diverse materials with aggregation induced emission (AIE) and significant mechanochromic performance by employing D-π-A structures with large dipole moments. Mechanochromic luminescence: Three tetra-aryl substituted 1,3-butadiene derivatives with distinct electronic push and/or pull substituents have been prepared. All three derivatives show typical aggregation enhanced emission (AEE) features owing to the restriction of intramolecular rotations. The results demonstrate that chromophores with both large dipole moments and AEE characteristics are of benefit for mechanochromic applications with efficient solid-state emissions.
- Zhang, Yijia,Han, Ting,Gu, Shangzhi,Zhou, Tianye,Zhao, Chuanzhen,Guo, Yuexin,Feng, Xiao,Tong, Bin,Bing,Shi, Jianbing,Zhi, Junge,Dong, Yuping
-
supporting information
p. 8856 - 8861
(2014/07/22)
-
- Selective deprotection of Me3Si-/Ph2P(O)-protected arylalkynes: Methyl Grignard reagent-promoted dephosphorylation of Ph2P(O)-protected alkynes
-
A Ph2P(O)-protected alkyne underwent dephosphorylation by treatment with MeMgBr in THF with Me3Si-protection untouched. The dephosphorylation followed by a transition-metal-catalyzed coupling of the resulting terminal a lkyne with aryl halides was carried out in a one-pot manner to afford the desired coupling product. Selective deprotection of Me3Si-/Ph2P(O)-protected alkynes enabled facile syntheses of expanded π-systems such as cyclic phenyleneethyny lenes and unsymmetrically substituted ditriazol.
- Peng, Lifen,Xu, Feng,Shinohara, Kenta,Orita, Akihiro,Otera, Junzo
-
supporting information
p. 1610 - 1612
(2014/12/11)
-
- Highly regioselective synthesis of substituted isoindolinones via ruthenium-catalyzed alkyne cyclotrimerizations
-
(Cyclooctadiene)(pentamethylcyclopentadiene) ruthenium chloride [Cp*RuCl (cod)] has been used to catalyze the regioselective cyclization of amide-tethered diynes with monosubstituted alkynes to give polysubstituted isoindolinones. Notably, the presence of a trimethylsilyl group on the diyne generally led to complete control over the regioselectivity of the alkyne cyclotrimerization. The cyclization reaction worked well in a sustainable non-chlorinated solvent and was tolerant of moisture. The optimized conditions were effective with a diverse range of alkynes and diynes. The 7-silylisoindolinone products could be halogenated, protodesilylated or ring opened to access a range of usefully functionalized products.
- Foster, Robert W.,Tame, Christopher J.,Hailes, Helen C.,Sheppard, Tom D.
-
p. 2353 - 2360
(2013/10/01)
-
- ANTIBACTERIAL AGENTS
-
Antibacterial compounds of formula (I) are provided, as well as stereoisomers and pharmaceutically acceptable salts thereof; pharmaceutical compositions comprising such compounds; methods of treating bacterial infections by the administration of such compounds; and processes for the preparation of such compounds.
- -
-
Page/Page column 86
(2013/12/03)
-
- ANTIBACTERIAL AGENTS
-
Antibacterial compounds of formula (I) are provided, as well as stereoisomers and pharmaceutically acceptable salts thereof; pharmaceutical compositions comprising such compounds; methods of treating bacterial infections by the administration of such compounds; and processes for the preparation of such compounds.
- -
-
Page/Page column 34
(2013/12/03)
-
- Palladium-catalyzed trifluoroethylation of terminal alkynes with 1,1,1-trifluoro-2-iodoethane
-
An efficient Csp-CH2CF3 bond-forming reaction via Pd-catalyzed 2,2,2-trifluoroethylation of aryl and alkyl terminal alkynes has been developed. This protocol proceeds under mild conditions using the readily available and cheap reagent CF3CH2I as the source of the CH2CF3 group. Various terminal aryl alkynes as well as alkylacetylenes can be transformed into the corresponding trifluoroethylated products in good-to-excellent yields. The method is tolerant of carbonyl, nitro, ester, cyano, and even formyl groups.
- Feng, Yi-Si,Xie, Chuan-Qi,Qiao, Wen-Long,Xu, Hua-Jian
-
supporting information
p. 936 - 939
(2013/03/28)
-
- Mn-catalyzed aromatic C-H alkenylation with terminal alkynes
-
The first manganese-catalyzed aromatic C-H alkenylation with terminal alkynes is described. The procedure features an operationally simple catalyst system containing commercially available MnBr(CO)5 and dicyclohexylamine (Cy2NH). The reaction occurs readily in a highly chemo-, regio-, and stereoselective manner delivering anti-Markovnikov E-configured olefins in high yields. Experimental study and DFT calculations reveal that (1) the reaction is initiated by a C-H activation step via the cooperation of manganese and base; (2) manganacycle and alkynylmanganese species are the key reaction intermediates; and (3) the ligand-to-ligand H-transfer and alkynyl-assisted C-H activation are the key steps rendering the reaction catalytic in manganese.
- Zhou, Bingwei,Chen, Hui,Wang, Congyang
-
supporting information
p. 1264 - 1267
(2013/03/14)
-
