- Synthesis of molecular tripods based on a rigid 9,9'-spirobifluorene scaffold
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The efficient synthesis of a new tripodal platform based on a rigid 9,9'-spirobifluorene with three acetyl protected thiol groups in the positions 2, 3' and 6' for deposition on Au(111) surfaces is reported. The modular 9,9'-spirobifluorene platform provi
- Valá?ek, Michal,Edelmann, Kevin,Gerhard, Lukas,Fuhr, Olaf,Lukas, Maya,Mayor, Marcel
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Read Online
- Surface-Guided Formation of an Organocobalt Complex
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Organocobalt complexes represent a versatile tool in organic synthesis as they are important intermediates in Pauson-Khand, Friedel-Crafts, and Nicholas reactions. Herein, a single-molecule-level investigation addressing the formation of an organocobalt c
- Weber, Peter B.,Hellwig, Raphael,Paintner, Tobias,Lattelais, Marie,Paszkiewicz, Mateusz,Casado Aguilar, Pablo,Deimel, Peter S.,Guo, Yuanyuan,Zhang, Yi-Qi,Allegretti, Francesco,Papageorgiou, Anthoula C.,Reichert, Joachim,Klyatskaya, Svetlana,Ruben, Mario,Barth, Johannes V.,Bocquet, Marie-Laure,Klappenberger, Florian
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- A "flexible" Rigid Rod, trans-Pt(PMe3)2(C-CC6H4CN)2 (L1), to Form 2D [{Cu2(μ2-X)2}2(μ4-L1)]n Polymers (X = Br, I) Exhibiting the Large
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The trans-Pt(PMe3)2(C-CC6H4CN)2 organometallic ligand L1, which is prepared from 4-ethynylbenzonitrile and cis-Pt(PMe3)2Cl2, binds CuX salts to form two strongly lumin
- Juvenal, Frank,Fortin, Daniel,Harvey, Pierre D.
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Read Online
- Effect of the π-bridge on the light absorption and emission in push-pull coumarins and on their supramolecular organization
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A family of eight π-extended push–pull coumarins with cross-conjugated (amide) and directly conjugated (p-phenylene, alkyne, alkene) bridges were synthesized through a convergent strategy. Using an experimentally calibrated computational protocol, their UV–Visible light absorption and emission spectra in solution were investigated. Remarkably, amide-, alkyne- and alkene-bridges undergo comparable vertical excitations. The different nature of these bridges manifests during excited-state relaxation and fluorescence. We predict that these molecules can serve as building blocks for p-type semiconductors with low reorganization energies, below 0.2 eV. Since solid-state self-assembly is crucial for this application, we examined the effect of the π-bridge over the supramolecular organization in this family of compounds to determine if stacking prevails in these π-extended coumarin derivatives. Amide and alkyne spacers allow coplanar conformations which crystallize readily; p-phenylene hinders planarity yet allows facile crystallization; alkene-bridged molecules eluded all crystallization attempts. All the crystals obtained feature dense face-to-face π-stacking with 3.5–3.7 ? interlayer distances, expected to facilitate charge transfer processes in the solid state.
- Arcos-Ramos, Rafael,Carreón-Castro, María del Pilar,Farfán, Norberto,González-Rodríguez, Edgar,Guzmán-Juárez, Brenda,Maldonado-Domínguez, Mauricio,Miranda-Olvera, Montserrat,Santillan, Rosa
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supporting information
(2021/11/08)
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- Iodonium Cation-Pool Electrolysis for the Three-Component Synthesis of 1,3-Oxazoles
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The synthesis of 1,3-oxazoles from symmetrical and unsymmetrical alkynes was realized by an iodonium cation-pool electrolysis of I2 in acetonitrile with a well-defined water content. Mechanistic investigations suggest that the alkyne reacts with the acetonitrile-stabilized I+ ions, followed by a Ritter-type reaction of the solvent to a nitrilium ion, which is then attacked by water. The ring closure to the 1,3-oxazoles released molecular iodine, which was visible by the naked eye. Also, some unsymmetrical internal alkynes were tested and a regioselective formation of a single isomer was determined by two-dimensional NMR experiments.
- Sattler, Lars E.,Hilt, Gerhard
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supporting information
p. 605 - 608
(2020/12/07)
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- Iron-Catalyzed Vinylzincation of Terminal Alkynes
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Organozinc reagents are among the most commonly used organometallic reagents in modern synthetic chemistry, and multifunctionalized organozinc reagents can be synthesized from structurally simple, readily available ones by means of alkyne carbozincation. However, this method suffers from poor tolerance for terminal alkynes, and transformation of the newly introduced organic groups is difficult, which limits its applications. Herein, we report a method for vinylzincation of terminal alkynes catalyzed by newly developed iron catalysts bearing 1,10-phenanthroline-imine ligands. This method provides efficient access to novel organozinc reagents with a diverse array of structures and functional groups from readily available vinylzinc reagents and terminal alkynes. The method features excellent functional group tolerance (tolerated functional groups include amino, amide, cyano, ester, hydroxyl, sulfonyl, acetal, phosphono, pyridyl), a good substrate scope (suitable terminal alkynes include aryl, alkenyl, and alkyl acetylenes bearing various functional groups), and high chemoselectivity, regioselectivity, and stereoselectivity. The method could significantly improve the synthetic efficiency of various important bioactive molecules, including vitamin A. Mechanistic studies indicate that the new iron-1,10-phenanthroline-imine catalysts developed in this study have an extremely crowded reaction pocket, which promotes efficient transfer of the vinyl group to the alkynes, disfavors substitution reactions between the zinc reagent and the terminal C–H bond of the alkynes, and prevents the further reactions of the products. Our findings show that iron catalysts can be superior to other metal catalysts in terms of activity, chemoselectivity, regioselectivity, and stereoselectivity when suitable ligands are used.
- Hu, Meng-Yang,Huang, Qiang,Su, Yu-Xuan,Sun, Wei,Wang, Wei-Na,Zhu, Shou-Fei
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supporting information
(2022/01/08)
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- Synthesis of alkynes under dry reaction conditions
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An easy synthetic method was developed under dry reaction conditions for the preparation of terminal alkynes from 1,1-dibromoalkenes and in the presence of succinimide which acts as a nucleophile and proton donor. It was demonstrated with the synthesis of a broad spectrum of terminal alkynes and extended to synthesize internal alkynes under tandem reaction conditions.
- Rao, Maddali L.N.,Shamim Islam, Sk
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supporting information
(2021/04/19)
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- Ratiometric sensing of fluoride ions using Raman spectroscopy
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Ratiometric Raman spectroscopy represents a novel sensing approach for the detection of fluoride anions based on alkyne desilylation chemistry. This method enables rapid, anion selective and highly sensitive detection of fluoride in a simple paper-based a
- Tipping, William J.,Wilson, Liam T.,Blaseio, Sonja K.,Tomkinson, Nicholas C. O.,Faulds, Karen,Graham, Duncan
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p. 14463 - 14466
(2020/12/01)
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- Fe-Catalyzed Selective Cyclopropanation of Enynes under Photochemical or Thermal Conditions
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The nucleophilic Fe-complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the cyclopropanation of enynes to substituted propargyl cyclopropanes using diazoesters as carbene surrogates. The catalyst can be activated either thermally in the presence of catalytic amounts of 4-nitroanisole or under photochemical conditions. Cyclopropanation occurs selectively at the enyne moiety; alternative olefinic moieties remain intact.
- Picher, Marie-Idrissa,Plietker, Bernd
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supporting information
p. 340 - 344
(2020/01/11)
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- Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
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There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
- Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
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p. 6299 - 6308
(2020/07/21)
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- Bisthiophene/triazole based 4,6-diamino-1,3,5-triazine triblock polyphiles: Synthesis, self-assembly and metal binding properties
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Two series of 4,6-diamino-1,3,5-triazine triblock polyphiles consisting of an extremely long bisthiophene/triazole based rigid cores, with flexible alkyl chains at one end and a polar 4,6-diamino-1,3,5-triazine at the other end were synthesized. Colh
- Liu, Chao,Gao, Hongfei,Li, Taihao,Xiao, Yulong,Cheng, Xiaohong
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p. 294 - 302
(2019/05/29)
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- Multicolor Cocktail for Breast Cancer Multiplex Phenotype Targeting and Diagnosis Using Bioorthogonal Surface-Enhanced Raman Scattering Nanoprobes
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Early precise diagnosis of cancers is crucial to realize more effective therapeutic interventions with minimal toxic effects. Cancer phenotypes may also alter greatly among patients and within individuals over the therapeutic process. The identification and characterization of specific biomarkers expressed on tumor cells are in high demand for diagnosis and treatment, but they are still a challenge. Herein, we designed three new bioorthogonal surface-enhanced Raman scattering (SERS) nanoprobes and successfully applied the cocktail of them for MDA-MB-231 and MCF-7 breast cancer multiplex phenotype detection. The SERS nanoprobes containing Raman reporters with diynl, azide, or cyano moieties demonstrated apparent Raman shift peaks in 2205, 2120, and 2230 cm-1, respectively, in the biologically Raman-silent region. Three target ligands, including oligonucleotide aptamer (AS1411), arginine-glycine-aspatic acid (RGD) peptide, and homing cell adhesion molecule antibody (anti-CD44), were separately conjugated to the nanoprobes for active recognition capability. The cocktail of the nanoprobes manifested minimal cytotoxicity and simultaneously multiplex phenotype imaging of MDA-MB-231 and MCF-7 cells. Quantitative measurement of cellular uptake by inductively coupled plasma mass spectrometry (ICPMS) verified that MDA-MB-231 cells harbored a much higher expression level of CD44 receptor than MCF-7 cells. For in vivo SERS detection, Raman shift peaks of 2120, 2205, and 2230 cm-1 in the micro-tumor were clearly observed, representing the existence of three specific biomarkers of nucleolin, integrin αvβ3, and CD44 reporter, which could be used for early cancer phenotype identification. The biodistribution results indicated that target ligand modified nanoprobes exhibited much more accumulation in tumors than those nanoprobes without target ligands. The multicolor cocktail of bioorthogonal SERS nanoprobes offers an attractive and insightful strategy for early cancer multiplex phenotype targeting and diagnosis in vivo that is noninvasive and has low cross-talk, unique spectral-molecular signature, high sensitivity, and negligible background interference.
- Wang, Jing,Liang, Duanwei,Feng, Jie,Tang, Xinjing
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p. 11045 - 11054
(2019/09/09)
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- Tuning alkynyl-extended 9,10-dihydroanthracene-based systems into aggregation-induced emission (AIE) luminophores
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A series of 9,10-bis(1,5-diphenylpenta-1,4-diyn-3-ylidene)-9,10-dihydroanthracenes (BDPPD-DHAs) carrying polar organic functional groups was synthesized through Sonogashira cross-coupling reactions. The structural and electronic properties of these BDPPD-
- Johnson, Matthew A.,Tabasi, Zahra A.,Zhao, Yuming
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p. 8325 - 8331
(2019/06/08)
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- DBU-Mediated Synthesis of Aryl Acetylenes or 1-Bromoethynylarenes from Aldehydes
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Two well known synthetic organic reactions Ramirez olefination and Corey-fuchs reactions are integrated in one-pot sequential manner for the synthesis of arylacetylenes and 1,3-enynes starting directly from commercially available aldehydes. The bicyclic amidine 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) along with additive NaOH not only exclusively afforded the terminal alkynes directly from the aldehydes, but also enhanced the reaction rate. The dynamic nature of DBU also facilitated the isolation of 1-bromoalkynes intermediate products. Selection of additive from NaOH and H2O served as a switch for the synthesis of terminal alkyne and 1-bromoalkynes, respectively. (Figure presented.).
- Thummala, Yadagiri,Karunakar, Galla V.,Doddi, Venkata Ramana
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supporting information
p. 611 - 616
(2019/01/04)
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- Gold-Catalyzed Hydrohydrazidation of Terminal Alkynes
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Facile gold-catalyzed hydrohydrazidation of alkynes with various hydrazides R2CONHNH2 (R = Alk or Ar; including those with an additional nucleophilic moiety) in the presence of Ph3PAuNTf2 (6 mol %) leading to a wide range of substituted keto-N-acylhydrazones (18 examples) in excellent to good yields (99-66%) is reported. This novel metal-catalyzed coupling proceeds under mild conditions (chlorobenzene, 60 °C), exhibits high functional group tolerance, and is insensitive to the electronic and steric effects of the substituents in the reactants.
- Zimin, Dmitry P.,Dar'In, Dmitry V.,Rassadin, Valentin A.,Kukushkin, Vadim Yu.
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supporting information
p. 4880 - 4884
(2018/08/24)
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- An Additive-Free, Base-Catalyzed Protodesilylation of Organosilanes
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We report an additive-free, base-catalyzed C-, N-, O-, and S-Si bond cleavage of various organosilanes in mild conditions. The novel catalyst system exhibits high efficiency and good functional group compatibility, providing the corresponding products in good to excellent yields with low catalyst loadings. Overall, this transition-metal-free process may offer a convenient and general alternative to current employing excess bases, strong acids, or metal-catalyzed systems for the protodesilylation of organosilanes.
- Yao, Wubing,Li, Rongrong,Jiang, Huajiang,Han, Deman
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p. 2250 - 2255
(2018/02/23)
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- α-Hydroxy-Tetrazoles as Latent Ethynyl Moieties: A Mechanistic Investigation
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This article focuses on the dehydration of α-hydroxy-tetrazoles, leading to tetraazafulvenes and then to vinylic carbenes that rearrange into ethynyl moieties through the Fritsch-Buttenberg-Wiechell rearrangement. Each step of this sequence was scrutinized, either by examination of the substrate and/or dehydrating agent scope, or through AM1 calculations, in order to understand the limiting step of this process. This underrated transformation appears to be a viable alternative to existing methods used for transforming aldehydes into alkynes.
- Quinodoz, Pierre,Wright, Karen,Drouillat, Bruno,Kletskii, Mikhail E.,Burov, Oleg N.,Lisovin, Anton. V.,Couty, Fran?ois
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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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- Deciphering micro-polarity inside the endoplasmic reticulum using a two-photon active solvatofluorochromic probe
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A new class of two-photon active and solvatofluorochromic dyes for the determination of ER polarity is reported. The fluorescent colour spans almost the entire visible spectrum. One of the derivatives is rationally designed for specific ER targeting. Finally, the fluorescence spectral scanning technique has been utilised to determine the micro-polarity inside the ER which is found to be much lower than that of water.
- Pal, Kaushik,Samanta, Indranil,Gupta, Rahul Kumar,Goswami, Debabrata,Koner, Apurba Lal
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supporting information
p. 10590 - 10593
(2018/09/27)
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- Synthesis method of benzonitrile compounds
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The invention provides a preparation method of benzonitrile compounds. The preparation method comprises the steps: carrying out a reaction in an organic solvent at 0-50 DEG C for 4-12h under the action of an oxidant by taking phenylacetylene as shown in the formula (I) and a derivative of phenylacetylene as raw materials and nitrite as a nitrogen source, and separating and purifying the obtained reaction liquid to prepare the benzonitrile compound as shown in the formula (II); and the amount-of-substance ratio of the nitrogen source to phenylacetylene as shown in the formula (I) and the derivative of phenylacetylene is (1-3):1. The preparation method is simple and available in raw material, mild in reaction condition, good in functional group tolerance, simple in operation and environment-friendly so as to be a novel method for synthesizing benzonitrile containing various substituent groups.
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Paragraph 0060; 0061; 0062
(2018/04/02)
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- Synthesis, photophysical and concentration-dependent tunable lasing behavior of 2,6-diacetylenyl-functionalized BODIPY dyes
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2,6-Diacetylenyl- and 2,6-bis(arylacetylenyl)-functionalized pentamethyl-difluoroborondipyrromethene (BODIPY) derivatives, namely, PBDP1 and PBDP2-4 (aryl = phenyl, 4-methoxyphenyl, or 4-cyanophenyl), respectively, which exhibit extended π-conjugation, were synthesized and characterized by various spectroscopic methods. Significant bathochromic shifts in both absorption and emission were observed upon modifying the structure of the BODIPY core via the strategy of extending its π-conjugation. The derivatives displayed efficient emission in the yellow-to-red spectral region, with a high fluorescence quantum yield and a relatively large Stokes shift. Under conditions of transverse pumping in a cuvette, PBDP1 and PBDP2 exhibited highly efficient and stable laser activity for up to 180 and 110 minutes of continuous irradiation, respectively. Amplified spontaneous emission (FWHM of ca. 2.5 nm) with an efficiency of 41% and 36% was achieved for PBDP1 and PBDP2, respectively, in toluene, which had tunable ranges of 561 to 580 nm and 602 to 617 nm, respectively, on irradiation with a Q-switched Nd:YAG laser at 532 nm. The lasing properties of PBDP3 and PBDP4, which contain electron-donating (-OMe) and electron-withdrawing (-CN) arylacetylenyl moieties, respectively, were also investigated. A corresponding digold(i) diacetylide organometallic complex, namely, (PPh3)Au-C≡C-BODIPY-C≡C-Au(PPh3) (PBDP5) was also synthesized and characterized to study the effect of Au(i). PBDP5 exhibited phosphorescence in the vis-NIR region centered at 751 nm at 77 K owing to heavy-atom-induced intersystem crossing.
- Maity, Apurba,Sarkar, Anirban,Sil, Amit,B. N., Shivakiran Bhaktha,Patra, Sanjib K.
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supporting information
p. 2296 - 2308
(2017/03/22)
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- Substituent Effects That Control Conjugated Oligomer Conformation through Non-covalent Interactions
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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.
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supporting information
p. 5164 - 5174
(2017/05/04)
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- A practical non-metal catalytic silicon of the amino protection of the new method (by machine translation)
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The invention relates to a high efficiency, mild organic silicon reagent carbon silicon key fracture of the new method. The method of this reaction to the alkali is cheap and easy to obtain metal catalyst, in order to common commercial solvent as a reaction solvent and a hydrogen source, in the air and in the under mild conditions can be successfully catalytic trimethyl aryl silicon reagent or aryl alkyne base silicon reagent selectively generating carbon silicon key cracking hydrogenation reaction, the substrate universality is wide, functional group compatibility outstanding. The first innovative to realize the non-transition metal catalyzed carbon silicon key breaking reaction, also overcome the traditional method requires the use of greatly excessive inorganic alkali or an expensive metal catalyst to the limitation of the silicon of the amino protection, for the laboratory preparation and industry in the production of the organosilicon group deprotection provides a completely new strategy. (by machine translation)
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Paragraph 0070; 0071
(2018/04/01)
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- Efficient one-pot synthesis of 1-chlorovinyl p-tolyl sulfoxides from aldehydes and ketones by the Horner-Wadsworth-Emmons reaction
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A variety of 2-monosubstituted and 2,2-disubstituted 1-chlorovinyl p-tolyl sulfoxides was synthesized through a one-pot procedure by the Horner-Wadsworth-Emmons reaction of carbonyl compounds with [chloro(diethoxyphosphoryl)(p-tolylsulfinyl)methyl]lithium, which was generated from diethyl chlorophosphate, chloromethyl p-tolyl sulfoxide, and lithium diisopropylamide in advance. The in situ-prepared sulfoxides were directly converted into alkynes via the sulfoxide/magnesium exchange reaction with i-PrMgCl and the subsequent Fritsch-Buttenberg-Wiechell rearrangement of the resulting magnesium alkylidene carbenoids.
- Kimura, Tsutomu,Kobayashi, Gen,Ijima, Shiori,Saito, Sae,Imafuji, Aki,Satoh, Tsuyoshi
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- A copper (II) (II) composite chlorinating agent and copper-based composite chlorinating agent synthesis of 1-chloro-2-aryl acetylene method
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The invention discloses a copper (II) composite chlorinating agent and a method for synthesizing 1-chlorine-2-aryl acetylene based on the copper (II) composite chlorinating agent. The structural formula of the copper (II) composite chlorinating agent is CuCl2.xNaCl.yAl2O3. The chlorinating agent is applicable to chlorination of various substituted aryl acetylene substrates, and is high in universality; the chlorinating agent can directly carry out chlorination reaction on aryl acetylene so as to obtain a 1-chlorine-2-aryl acetylene product; the method is mild in reaction condition, 1-chlorine-2-aryl acetylene can be synthesized with high yield and high selectivity, and the production cost of the 1-chlorine-2-aryl acetylene derivative is greatly lowered.
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Paragraph 0023; 0122; 0123
(2016/11/24)
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- The design of liquid crystalline bistolane-based materials with extremely high birefringence
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We designed three new bistolanes with alkylsulfanyl groups. A symmetric derivative contains short terminal methylsulfanyl groups (-SCH3) on both ends, while two asymmetric derivatives contain a methylsulfanyl group on one end, as well as a highly polarizable cyano (-CN) or isothiocyanate (-NCS) group on the other end. These materials exhibited a well-defined enantiotropic nematic phase, as well as an extremely high birefringence (Δn > 0.6). Most notably, the NCS derivative achieves an extremely high value of 0.77 at 550 nm. These results should be helpful for the design and synthesis of novel nematic materials with high birefringence.
- Arakawa, Yuki,Kang, Sungmin,Tsuji, Hideto,Watanabe, Junji,Konishi, Gen-Ichi
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p. 92845 - 92851
(2016/10/11)
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- ALKYNE COMPOUNDS AS S-NITROSOGLUTATHIONE REDUCTASE INHIBITORS
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Provided are compounds of formula (Ia) and pharmaceutically acceptable salts thereof, wherein A, B, R 1, R 2, m and n are as defined herein, which are active as inhibitors of S-Nitrosoglutathione reductase (GSNOR). These compounds prevent, inhibit, or suppress the action of GSNOR and are therefore useful in the treatment of GSNOR mediated diseases, disorders, syndromes or conditions such as, e.g., pulmonary hypertension, acute respiratory distress syndrome (ARDS), asthma, bronchospasm, cough, pneumonia, pulmonary fibrosis, interstitial lung diseases, cystic fibrosis and chronic obstructive pulmonary disease (COPD).
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Page/Page column 60
(2016/05/02)
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- Cleavage of the Carbon–Carbon Triple Bonds of Arylacetylenes for the Synthesis of Arylnitriles without a Metal Catalyst
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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
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supporting information
p. 3056 - 3059
(2016/07/12)
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- Fluoranthene derivatives as blue fluorescent materials for non-doped organic light-emitting diodes
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In this study, we report synthesis of symmetrically and non-symmetrically functionalized fluoranthene-based blue fluorescent molecular materials for non-doped electroluminescent devices. The solid state structure of these fluorophores has been established
- Kumar, Shiv,Kumar, Deepak,Patil, Yogesh,Patil, Satish
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supporting information
p. 193 - 200
(2015/12/30)
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- Two-dimensional bricklayer arrangements of tolans using halogen bonding interactions
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Diphenylacetylene (tolan) derivatives with self-complementary aryl halides and halogen bond-accepting nitriles form 2D bricklayer packing motifs when halogen bonding occurs. When halogen bonding is absent, as occurred with fluorinated aryl bromides, the molecules adopt other packing motifs. These results suggest halogen bonding is potentially useful for producing rarely observed 2D bricklayer motifs in organic semiconductors.
- Frausto, Fanny,Smith, Zachary C.,Haas, Terry E.,Thomas, Samuel W.
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supporting information
p. 8825 - 8828
(2015/05/20)
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- Two Symmetrically Bis-substituted Pyrene Derivatives: Synthesis, Photoluminescence, and Electroluminescence
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Two kinds of cyanophenyl terminated pyrene derivatives for organic light-emitting diodes were synthesized and characterized by UV/Vis, fluorescence (FL), 1H NMR, MALDI-TOF, CV and TGA. Both compounds exhibited blue photoluminescence and high fluorescent quantum yield of 85% and 75% in solutions. Due to the presence of acetylene spacer, the compound distinguishes itself by high coplanarity, high thermal stability, little Stokes' shift and clear excimer formation in the solid state from the acetylene-free compound. In order to suppress the molecular aggregation, the electroluminescent properties were studied by doing the materials in PVK. The result proved that energy transfer happened from the host PVK to the materials. Two kinds of cyanophenyl terminated pyrene derivatives for OLEDs were synthesized and characterized. Both compounds exhibited blue photoluminescence and high fluorescent quantum yield of 85% and 75% in solutions. The result proved that energy transfer happened from the host PVK to the materials.
- Gong, Xiaojie,Xie, Xiang,Chen, Naiwu,Zheng, Chaoyue,Zhu, Jie,Chen, Runfeng,Huang, Wei,Gao, Deqing
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p. 967 - 973
(2015/09/01)
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- Tunable electron acceptors based on cyclopenta[hi]aceanthrylenes
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A series of substituted cyclopenta[hi]aceanthrylene derivatives with electron donating (NH2, OCH3), neutral (H), and electron withdrawing (COOH, CF3, CN, NO2) substituents were prepared. A room-temperature Sonogashira cross-coupling reaction between 2,7-dibromocyclopenta[hi]aceanthrylene and an appropriately functionalized phenylene ethynylene precursor was utilized to access the materials that were characterized by Nuclear Magnetic Resonance Spectroscopy (NMR), cyclic voltammetry (CV), and UV-Vis spectroscopy. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were systematically varied when proceeding from electron donating to electron withdrawing substituents. The optical band gap was significantly altered for the most electron donating species, while little change was observed between different electron withdrawing substituents. This study demonstrates the ability to control the frontier orbital energies of this class of cyclopenta-fused polycyclic aromatic hydrocarbon materials through selective substitution.
- Zhu, Xinju,Yuan, Bingxin,Plunkett, Kyle N.
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supporting information
p. 7105 - 7107
(2015/12/01)
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- An efficient method for the production of terminal alkynes from 1,1-dibromo-1-alkenes and its application in the total synthesis of natural product dihydroxerulin
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An efficient method of preparing various terminal alkynes from 1,1-dibromo-1-alkenes by using TBAF (tetra-n-butylammonium fluoride) as a base and triphenylphosphane as a reductant was developed. This method is strong base and low/high temperatures free, and can tolerate a broad range of substrates. These advantages were well demonstrated by the application of this method to the total synthesis of polyene natural product dihydroxerulin.
- Liu, Shihui,Chen, Xiaobei,Hu, Yanwei,Yuan, Laiqi,Chen, Shaohua,Wu, Ping,Wang, Wei,Zhang, Shilei,Zhang, Wei
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p. 553 - 560
(2015/03/05)
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- The Dual Role of 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) in the Synthesis of Terminal Aryl- and Styryl-Acetylenes via Umpolung Reactivity
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The dual role of the bicyclic amidine base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was demonstrated in a synthesis of terminal aryl- and styryl-acetylenes. Mechanistically, a tandem process involving elimination/Umpolung/protonation occurs in a single step to generate terminal aryl- and styryl-acetylenes from geminal dibromoalkenes. The key to the success of this transformation lies in the organobase-mediated generation of the acetylide from the 1-bromoalkynes at room temperature. The unique characteristics of DBU as an inherently safer reagent make it an attractive alternative to previous systems wherein required pyrophoric reagents and nonambient temperatures remain unsolved issues. The procedure does not work for the synthesis of alkyl-acetylenes.
- Morri, Ashok Kumar,Thummala, Yadagiri,Doddi, Venkata Ramana
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supporting information
p. 4640 - 4643
(2015/09/28)
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- Nucleophilic substitution in 16π-antiaromatic system: Synthesis of heteroatom-substituted dibenzopentalenes
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An antiaromatic compound, 5-bromo-10-iododibenzopentalene, underwent nucleophilic substitution of heteroatoms such as R2NLi, ROLi, and RSLi. This subst itution proceeded preferentially at the bromopentalene moiety than at the iodo-counterpart.
- Xu, Feng,Peng, Lifen,Wakamatsu, Kan,Orita, Akihiro,Otera, Junzo
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supporting information
p. 1548 - 1550
(2015/02/19)
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- A versatile and highly efficient method for 1-chlorination of terminal and trialkylsilyl-protected alkynes
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A highly efficient one-pot procedure for the preparation of 1-chloroalkynes and 1-chlorobutadiynes from terminal and trialkylsilyl-protected precursors is reported. This convenient reaction, proceeding under mild conditions, utilizes N-chlorosuccinimide as the chlorinating agent and tolerates a range of functional groups. A general chlorination of alkynes: A highly efficient one-pot procedure for the preparation of 1-chloroalkynes and 1-chlorobutadiynes from terminal and trialkylsilyl-protected precursors is reported (see figure; TMS=trimethylsilyl, TES=triethylsilyl, TBDMS=tert-butyldimethylsilyl, TIPS=triisopropylsilyl). This convenient reaction, proceeding under mild conditions, utilizes N-chlorosuccinimide as the chlorinating agent and tolerates a range of functional groups.
- Gulia, Nurbey,Pigulski, Bartlomiej,Charewicz, Marta,Szafert, Slawomir
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supporting information
p. 2746 - 2749
(2014/03/21)
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- Ti(OiPr)4/nBuLi: An attractive reagent system for [2+2+2] cyclotrimerisation reactions
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A convenient method for the [2+2+2] cyclotrimerisation of alkynes using Ti(OiPr)4/nBuLi is presented. Homotrimerisation of arylacetylenes proceeds within minutes with excellent regioselectivity. Moreover, the intermolecular construction of ABB heterotrimers can be achieved selectively from two different alkynes with similar electronic properties. The method is also suitable for the synthesis of pyridines.
- Rassadin,Nicolas,Six
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supporting information
p. 7666 - 7669
(2014/07/08)
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- Aerobic oxynitration of alkynes with tBuONO and TEMPO
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An efficient method for stereoselective nitroaminoxylation of alkyne has been reported. The reaction enjoys a broad substrate scope, good functional group tolerance, and high yields. Synthetically useful α-nitroketones can be accessed through these products in a single step.
- Dutta, Uttam,Maity, Soham,Kancherla, Rajesh,Maiti, Debabrata
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supporting information
p. 6302 - 6305
(2015/02/19)
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- Halogen bonding of (iodoethynyl)benzene derivatives in solution
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Halogen bonding (XB) between (iodoethynyl)benzene donors and quinuclidine in benzene affords binding free enthalpies (δG, 298 K) between -1.1 and -2.4 kcal mol-1, with a strong LFER with the Hammett parameter σpara. The enthalpic dri
- Dumele, Oliver,Wu, Dino,Trapp, Nils,Goroff, Nancy,Diederich, Francois
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supporting information
p. 4722 - 4725
(2015/04/27)
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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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- Antiprotozoal activity of dicationic 3,5-diphenylisoxazoles, their prodrugs and aza-analogues
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Fifty novel prodrugs and aza-analogues of 3,5-bis(4-amidinophenyl)isoxazole and its derivatives were prepared. Eighteen of the 24 aza-analogues exhibited IC50 values below 25 nM against Trypanosoma brucei rhodesiense or Plasmodium falciparum. S
- Patrick, Donald A.,Bakunov, Stanislav A.,Bakunova, Svetlana M.,Wenzler, Tanja,Brun, Reto,Tidwell, Richard R.
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p. 559 - 576
(2014/01/17)
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- Ferrocenes bearing highly extended π systems with nitrile, nitro, and dimethylamino end groups
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Oligophenylene-ethynylenes are a popular class of molecular wires for molecular electronics. Replacement of some, not all, of the 1,4-phenylene units by 1,1′-ferrocenylene moieties generates less rigid entities with a limited conformational flexibility. Within this concept, the syntheses of some 1,1′-disubstituted ferrocenes that bear arylethynyl or 4-(arylethynyl)phenyl substituents is presented. In contrast to related compounds with sulfur end groups that were prepared previously, the versions presented here have nitrile end groups, which, according to reported precedence, may serve as points of attachment to gold surfaces. A crystal structure analysis of an unusual diferrocenylethyne derivative is included. In addition, one representative with a push-pull disubstitution that has a nitro and a dimethylamino end group is presented. Many of the prepared compounds have been characterized by cyclic voltammetry. New ferrocenes bearing highly extended π systems with nitrile, nitro, and dimethylamino end groups are prepared that include a push-pull-substituted system. The redox properties of the new compounds have been characterized by cyclic voltammetry.
- Krau?e, Nico,Butensch?n, Holger
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p. 6686 - 6695
(2016/02/18)
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- Palladium-catalyzed trifluoroethylation of terminal alkynes with 1,1,1-trifluoro-2-iodoethane
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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
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supporting information
p. 936 - 939
(2013/03/28)
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- Dihalo-substituted dibenzopentalenes: Their practical synthesis and transformation to dibenzopentalene derivatives
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Diiodo- and bromo, iodo-substituted dibenzopentalenes were obtained by treatment of 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctene with I2 and IBr, respectively. These dihalo-substituted pentalenes reacted with terminal ethynes in Sonogashira co
- Xu, Feng,Peng, Lifen,Orita, Akihiro,Otera, Junzo
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supporting information; experimental part
p. 3970 - 3973
(2012/10/08)
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- Rapid consecutive three-component coupling-Fiesselmann synthesis of luminescent 2,4-disubstituted thiophenes and oligothiophenes
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(Hetero)aroyl chlorides, alkynes, and ethyl 2-mercapto acetate can be reacted in a consecutive three-component synthesis to give 2,4-disubstituted thiophene 5-carboxylates in good to excellent yields. In the sense of a pseudo-five-component reaction highly blue luminescent symmetrical terthiophenes and a quinquethiophene can be synthesized in excellent yield.
- Teiber, Marco,Mueller, Thomas J. J.
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supporting information; experimental part
p. 2080 - 2082
(2012/03/10)
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- Specific interaction modes in the crystal structures of oligofluorinated tolanes featuring additional electron donor and acceptor groups
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A series of partially fluorinated and specifically para-substituted tolanes (1-4) have been synthesized via palladium-catalyzed Sonogashira cross-coupling reaction. The single-crystal structures have been determined by X-ray diffraction. The molecules ado
- Stein, Mario,Berger, Ricarda,Seichter, Wilhelm,Hulliger, Jürg,Weber, Edwin
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scheme or table
p. 231 - 239
(2012/04/04)
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- General and selective head-to-head dimerization of terminal alkynes proceeding via hydropalladation pathway
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A general highly regio- and stereoselective palladium-catalyzed head-to-head dimerization reaction of terminal acetylenes is presented. This methodology allows for the efficient synthesis of a variety of 1,4-enynes as single E stereoisomers. Computational studies reveal that this dimerization reaction proceeds via the hydropalladation pathway.
- Jahier, Claire,Zatolochnaya, Olga V.,Zvyagintsev, Nickolay V.,Ananikov, Valentine P.,Gevorgyan, Vladimir
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supporting information; experimental part
p. 2846 - 2849
(2012/07/17)
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- Synthesis, characterization, and solid-state polymerization of cross-conjugated octatetraynes
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Two series of cross-conjugated 1,3,5,7-octatetraynes (1a-1l and 6a-6d) have been synthesized. UV-vis spectroscopic analysis shows that pendent groups connected to the cross-conjugated skeleton have little effect on the λmax energies, irrespective of whether the groups are electron withdrawing or donating. A number of the isolated products readily give crystals suitable for X-ray crystallography, and the solid-state structural properties of five derivatives (1k, 1l, 6a, 6c, and 6d) have been examined by X-ray crystallographic analysis. Parallel packing of the polyynes in the solid state indicates that four of the five samples are potentially suitable for topochemical polymerization, based on solid-state packing parameters θ, R, and d. Attempts to effect a solid-state reaction have been explored through UV-vis and γ-ray irradiation as well as thermal heating. The course of these reactions was monitored by differential scanning calorimetry (DSC) analysis, as well as UV-vis and solid-state 13C NMR spectroscopy (for 1d, 1j, 1k, and 6d), which offered evidence of polymer formation from these reactions. Structural determination of the product(s), however, remains elusive.
- Zhao, Yuming,Luu, Thanh,Bernard, Guy M.,Taerum, Tyler,McDonald, Robert,Wasylishen, Roderick E.,Tykwinski, Rik R.
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p. 994 - 1014
(2013/02/22)
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- One-pot, two-step conversion of aldehydes to phosphonyl- and sulfonylpyrazoles using Bestmann-Ohira reagent
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A one-pot, two-step, three-component method for the conversion of commercially available aldehydes to phosphonylpyrazoles has been developed, demonstrating, for the first time, the dual reactivity of the Bestmann-Ohira reagent (BOR) in a single-pot transformation. This method, extended to the synthesis of sulfonylpyrazoles by employing BOR in the first step and a diazomethyl sulfone in the second step, is complementary, with regard to regioselectivity, to the previous methods for the synthesis of such functionalized pyrazoles.
- Kumar, Rahul,Verma, Deepti,Mobin, Shaikh M.,Namboothiri, Irishi N. N.
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supporting information; experimental part
p. 4070 - 4073
(2012/09/21)
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- OPE/OPV H-mers: Synthesis, electronic properties, and spectroscopic responses to binding with transition metal ions
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A new type of structurally defined H-shaped OPE/OPV co-oligomers (termed H-mers) functionalized with various donor and/or acceptor end groups was synthesized by iterative Sonogashira coupling and Horner-Wadsworth-Emmons (HWE) reactions. Electronic substitution effects on the H-mer backbone were investigated by UV-vis absorption and fluorescence spectroscopy. Some H-mers were found to show spectral responses upon binding to an acid (TFA) or transition metal ions, revealing the applicability of H-mers in the field of chromophore and fluorophore based chemosensors.
- Zhou, Ningzhang,Wang, Li,Thompson, David W.,Zhao, Yuming
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supporting information; experimental part
p. 125 - 143
(2011/03/17)
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