- Phosphine-based push-pull AIE fluorophores: Synthesis, photophysical properties, and TD-DFT studies
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Herein, we report the design and characterization of a novel series of four push-pull fluorophores using diphenylphosphino as an electron-donating terminal group (P-chromophores). The spectroscopic properties in solution, the aggregation-induced emission
- Andraud, Chantal,Bretonnière, Yann,Colinet, Pauline,Jeanneau, Erwan,Le Bahers, Tangui,Rémond, Maxime
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- I2-mediated photochemical preparation of 2-substituted 1,3-dioxolanes and tetrahydrofurans from alcohols with polymer-supported hypervalent iodine reagent, PSDIB
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Various 2-substituted 1,3-dioxolanes, 1,3-dioxanes, and tetrahydrofurans were obtained selectively in good to moderate yields from the corresponding alcohols with PSDIB in the presence of iodine under irradiation conditions. Moreover, PSDIB was repeatedly used for the same reactions keeping good yield of the cyclic product.
- Teduka, Tomomasa,Togo, Hideo
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- Acetalization of aldehydes and ketones over H4[SiW 12O40] and H4[SiW12O 40]/SiO2
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H4[SiW12O40] (H-SiW12) is demonstrated to be able to efficiently catalyze the acetalization of aldehydes and ketones with ethylene glycol and 1,3-propanediol. Nevertheless, the possible leaching and the recycling of H-SiW12 are two major disadvantages that largely restrict its further application in industry. Moreover, H 4[SiW12O40] tends to deactivate strong proton sites due to the small surface area of 10 m2 g-1. Due to interactions with surface silanol groups, the proton sites of polyoxometalates (POMs) on SiO2 are less susceptible to deactivation. As such, immobilization of H4[SiW12O40] onto SiO 2 leads to the heterogeneous catalyst H4[SiW 12O40]/SiO2 (H-SiW12/SiO 2), which can catalyze the acetalization of aldehydes and ketones with ethylene glycol and 1,3-propanediol selectively and efficiently without the need of a drying agent. The acetalization process can proceed smoothly at a relatively low temperature under solvent-free conditions. The catalyst of H 4[SiW12O40]/SiO2 can be recycled at least ten times without an obvious decrease in its catalytic activity. As far as we know, the TONs of the H-SiW12/SiO2-catalyzed acetalization of cyclohexanone with ethylene glycol, and benzaldehyde with 1,3-propanediol are the highest reported so far.
- Zhao, Shen,Jia, Yueqing,Song, Yu-Fei
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- Anode interlayer in organic photovoltaics: Narrow bandgap small molecular materials as exciton-blocking layer
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Six materials were used as an interlayer at the anode side (anode interlayer [AIL]) of an archetypical planar heterojunction organic solar cell (OSC). In addition to two conventional wide bandgap hole transport materials (HTMs), tris(4-carbazol-9-ylphenyl
- Golder, Jan,Lin, Chiao-Wen,Chen, Chin-Ti
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- Synthesis of valsartan via decarboxylative biaryl coupling
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(Chemical Equation Presented) An efficient synthesis of the angiotensin II inhibitor valsartan (Diovan) is presented. Two routes were evaluated, both making use of an advanced version of our decarboxylative coupling for the construction of the biaryl moiety. Thus, in the presence of a catalyst system consisting of copper(II) oxide, 1,10-phenanthroline, and palladium(II) bromide, 2-cyanocarboxylic acid was coupled with 1-bromo(4-dimethoxymethyl)benzene in 80% yield and with 4-bromotoluene in 71% yield. The valsartan synthesis using 1-bromo(4-dimethoxymethyl)benzene was completed in four steps overall with a total yield of 39%, via a novel route that presents substantial economical and ecological advantages over the literature process, as it is more concise and stoichiometric amounts of expensive organometallic reagents are avoided.
- Goossen, Lukas J.,Melzer, Bettina
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- Driving an equilibrium acetalization to completion in the presence of water
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Formation of an acetal from a carbonyl substrate by condensation with an alcohol is a classical reversible equilibrium reaction in which the water formed must be removed to drive the reaction to completion. A new method has been developed for acetalization of carbonyl substrates by diols in the presence of water. Complexation of poly(4-styrenesulfonic acid) with poly(4-vinylpyridine) generates a catalytic membrane of polymeric acid at the interface between two parallel laminar flows in a microchannel of a microflow reactor. The catalytic membrane provides a permeable barrier between the organic layer and water-containing layer in the reaction, and permits discharge of water to the outlet of the microreactor to complete the acetalization. Condensation of a variety of carbonyl substrates with diols proceeded in the presence of water in the microflow device to give the corresponding acetals in yields of up to 97% for residence times of 19 to 38 s. the Partner Organisations 2014.
- Minakawa, Maki,Yamada, Yoichi M. A.,Uozumi, Yasuhiro
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- Carbosulfenylation of Alkenes with Organozinc Reagents and Dimethyl(methylthio)sulfonium Trifluoromethanesulfonate
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The electrophilic alkylthiolation of alkenes, initiated by dimethyl(methylthio)sulfonium salts and the subsequent addition of various heteronucleophilies has been well-established. Regarding the use of carbon nucleophiles, however, only carefully designed sp-type carbon sources have been successfully applied. We herein present our findings on the methylthiolation of alkenes with dimethyl(methylthio)sulfonium trifluoromethanesulfonate, followed by carbon-carbon bond formation in the presence of organozinc reagents, thus achieving a catalyst-free protocol toward to the carbosulfenylation of alkenes.
- Tang, Meizhong,Han, Shuxiong,Huang, Shenglan,Huang, Shenlin,Xie, Lan-Gui
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- Bis(perfluorooctanesulfonyl)imide supported on fluorous silica gel: Application to protection of carbonyls
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The immobilization of bis(perfluorooctanesulfonyl)imide (HNPf2) on fluorous silica gel (FSG) and its utilization in protection of carbonyls have been investigated. This system is reasonably general and can be applied to converting several carbonyls to the corresponding acetals and ketals in good to excellent yields. There is no need for the use of anhydrous solvents or inert atmosphere. Recycling studies have shown that the FSG-supported HNPf2 catalyst can be readily recovered and reused several times without significant loss of activity.
- Hong, Mei,Xiao, Guomin
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- Complete Monitoring of Coherent and Incoherent Spin Flip Domains in the Recombination of Charge-Separated States of Donor-Iridium Complex-Acceptor Triads
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The spin chemistry of photoinduced charge-separated (CS) states of three triads comprising one or two triarylamine donors, a cyclometalated iridium complex sensitizer and a naphthalene diimide (NDI) acceptor, was investigated by transient absorption spectroscopy in the ns-μs time regime. Strong magnetic-field effects (MFE) were observed for two triads with a phenylene bridge between iridium complex sensitizer and NDI acceptor. For these triads, the lifetimes of the CS states increased from 0.6 μs at zero field to 40 μs at about 2 T. Substituting the phenylene by a biphenyl bridge causes the lifetime of the CS state at zero field to increase by more than 2 orders of magnitude (τ = 79 μs) and the MFE to disappear almost completely. The kinetic MFE was analyzed in the framework of a generalized Hayashi-Nagakura scheme describing coherent (S, T0 虠 T±) as well as incoherent (S, T0 ? T±) processes by a single rate constant k±. The magnetic-field dependence of k± of the triads with phenylene bridge spans 2 orders of magnitude and exhibits a biphasic behavior characterized by a superposition of two Lorentzians. This biphasic MFE is observed for the first time and is clearly attributable to the coherent (B 10 mT) and incoherent (10 mT B 2 T) domains of spin motion induced by isotropic and anisotropic hyperfine coupling. The parameters of both domains are well understood in terms of the structural properties of the two triads, including the effect of electron hopping in the triad with two donor moieties. The kinetic model also accounts for the reduction of the MFE on reducing the rate constant of charge recombination in the triad with the biphenyl bridge. (Graph Presented).
- Klein, Johannes H.,Schmidt, David,Steiner, Ulrich E.,Lambert, Christoph
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- Triphenylphosphine-Based Covalent Organic Frameworks and Heterogeneous Rh-P-COFs Catalysts
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The synthesis of phosphine-based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine-based COFs (termed P-COFs) with well-defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P-COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine-based COF family, but also demonstrates their application in immobilizing homogeneous metal-based (e.g., Rh-phosphine) catalysts for application in heterogeneous catalysis.
- Liu, Yubing,Dikhtiarenko, Alla,Xu, Naizhang,Sun, Jiawei,Tang, Jie,Wang, Kaiqiang,Xu, Bolian,Tong, Qing,Heeres, Hero Jan,He, Songbo,Gascon, Jorge,Fan, Yining
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- Synthesis and Characterization of New Conjugated Fluorenyl-Porphyrin Dendrimers for Optics
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A new family of conjugated meso-tetraphenylporphyrin-based dendrimers with four (TPP1, TPP2), eight (TPP3, TPP4, TPP5) and up to sixteen (TPP6) fluorenyl groups has been synthesized and fully characterized. These tetraphenylporphyrin-cored dendrimers pres
- Yao, Dandan,Zhang, Xu,Mongin, Olivier,Paul, Frédéric,Paul-Roth, Christine O.
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- Dynamic Nuclear Polarization of Metal-Organic Frameworks Using Photoexcited Triplet Electrons
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While dynamic nuclear polarization based on photoexcited triplet electrons (triplet-DNP) has the potential to hyperpolarize nuclear spins of target substrates in the low magnetic field at room temperature, there has been no triplet-DNP system offering str
- Fujiwara, Saiya,Hosoyamada, Masanori,Tateishi, Kenichiro,Uesaka, Tomohiro,Ideta, Keiko,Kimizuka, Nobuo,Yanai, Nobuhiro
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- Argentivorous Molecules with Chromophores in Side Arms: Silver Ion-Induced Turn on and Turn off of Fluorescence
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The synthesis of argentivorous molecules (L1 and L2) having two chromophores (4-(anthracen-9-yl)benzyl or 4-(pyren-1-yl)benzyl groups) and two benzyl groups and the fluorescence properties of their silver complexes in a solution and the solid state are reported. A crystallographic approach for the Ag+ complexes with L1 and L2 revealed that the observed fluorescence changes stem from the excimer formation and extinction of fluorescent. Furthermore, binding stabilities of L1 and L2 toward Ag+ ions were estimated by the Ag+-induced UV-vis and PL spectral changes.
- Ju, Huiyeong,Taniguchi, Aya,Kikukawa, Kaoru,Horita, Hiroki,Ikeda, Mari,Kuwahara, Shunsuke,Habata, Yoichi
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- Application of poly(Vinylbenzyltrimethylammonium tribromide) resin as an efficient polymeric catalyst in the acetalization and diacetylation of benzaldehydes
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The applications of a new supported tribromide reagent (poly(vinylbenzyltrimethylammonium tribromide) resin) were reported. This supported tribromide resin was used as a catalyst in the acetalization and diacetylation of benzaldehydes under mild conditions with high efficiency. The effects of solvents, and amount of the supported tribromide resin on the reactions were investigated. Under the optimal conditions, most of acetal and 1,1-diacetates of benzaldehydes were selectively obtained in excellent yields.
- Han, Bingbing,Hu, Junjun,Li, Xianwei,Zheng, Zubiao
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supporting information
p. 287 - 293
(2021/04/28)
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- Synthesis and characterization of [4-{(CH2O)2CH}C6H4]2Hg, [4-(O=CH)C6H4]2Hg and [(E)-4-(RN=CH)C6H4]2Hg (R = 2′-py, 4′-py, 2′-pyCH
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The reaction of 4-[(CH2O)2CH]C6H4Br (1) with n-BuLi, followed by addition of HgCl2 to the in situ formed organolithium derivative, affords [4-{(CH2O)2CH}C6H4/sub
- Kiss, Levente,Pop, Alexandra,Shova, Sergiu,Ra?, Ciprian I.,Silvestru, Cristian
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- Synthesis and Evaluation of PPARδAgonists That Promote Osteogenesis in a Human Mesenchymal Stem Cell Culture and in a Mouse Model of Human Osteoporosis
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We synthesized a directed library of compounds to explore the structure-activity relationships of peroxisome proliferator-activated receptor δ(PPARδ) activation relative to mesenchymal stem cell (MSC) osteogenesis. Our scaffold used para-substituted cinnamic acids as a polar headgroup, a heteroatom and heterocycle core connecting units, and substituted phenyl groups for the lipophilic tail. Compounds were screened for their ability to increase osteogenesis in MSCs, and the most promising were examined for subunit specificity using a quantitative PPAR transactivation assay. Six compounds were selected for in vivo studies in an ovariectomized mouse model of human postmenopausal osteoporosis. Four compounds improved bone density in vivo, with two (12d and 31a) having activity comparable to that of GW0742, a well-studied PPARδ-selective agonist. 31a (2-methyl-4-[N-methyl-N-[5-methylene-4-methyl-2-[4-(trifluoromethyl)phenyl]thiazole]]aminocinnamic acid) had the highest selectivity for PPARδcompared to other subtypes, its selectivity far exceeding that of GW0742. Our results confirm that PPARδis a new drug target for possible treatment of osteoporosis via in situ manipulation of MSCs.
- Kress, Brian J.,Kim, Dong Hyun,Mayo, Jared R.,Farris, Jeffery T.,Heck, Benjamin,Sarver, Jeffrey G.,Andy, Divya,Trendel, Jill A.,Heck, Bruce E.,Erhardt, Paul W.
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p. 6996 - 7032
(2021/05/29)
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- Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
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Herein, a Grubbs-catalyzed route for the synthesis of nitriles via the aerobic oxidation of primary amines is reported. This reaction accommodates a variety of substrates, including simple primary amines, sterically hindered β,β-disubstituted amines, allylamine, benzylamines, and α-amino esters. Reaction compatibility with various functionalities is also noted, particularly with alkenes, alkynes, halogens, esters, silyl ethers, and free hydroxyl groups. The nitriles were also synthesized via the oxidation of imines generated from aldehydes and NH4OAc in situ. (Figure presented.).
- Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
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supporting information
p. 3583 - 3588
(2020/08/05)
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- COMPOSITION, COMPOSITION FOR DYNAMIC NUCLEAR POLARIZATION, POLARIZATION ENHANCING METHOD, HIGHLY POLARIZED SUBSTANCE, AND NMR MEASUREMENT METHOD
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A composition containing (1) a porous material and (2) a polarization source for dynamic nuclear polarization containing a molecule capable of being in an excited triplet state. According to the composition, a dynamic nuclear polarization system that has
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Paragraph 0156; 0157
(2020/12/14)
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- Boosting hydrogen evolution by using covalent frameworks of fluorinated cobalt porphyrins supported on carbon nanotubes
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A cobalt(ii) tetrakis(2,3,5,6-tetrafluoro-4-ethynylphenyl)porphyrin (FCoP-H) was designed and synthesized. With carbon-nanotube-templated polymerization, covalent porphyrin frameworks using FCoP-H can be synthesized via the Hay-coupling. The resulting FCo
- Xu, Gelun,Lei, Haitao,Zhou, Guojun,Zhang, Chaochao,Xie, Lisi,Zhang, Wei,Cao, Rui
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supporting information
p. 12647 - 12650
(2019/10/28)
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- Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals
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A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale.
- Allen, Benjamin D. W.,Hareram, Mishra Deepak,Seastram, Alex C.,McBride, Tom,Wirth, Thomas,Browne, Duncan L.,Morrill, Louis C.
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supporting information
p. 9241 - 9246
(2019/11/19)
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- The Hydrazine–O2 Redox Couple as a Platform for Organocatalytic Oxidation: Benzo[c]cinnoline-Catalyzed Oxidation of Alkyl Halides to Aldehydes
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An organocatalytic oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes is described. Commercially available benzo[c]cinnoline is shown to catalyze the oxidation of alkyl halides to aldehydes in a novel mechanistic paradigm involving nucleophilic attack, prototropic shift, and hydrolysis. The hydrolysis and reoxidation events occur readily with only adventitious oxygen and water. A survey of the scope of viable substrates is shown along with mechanistic and computational studies that give insight into this mode of catalysis.
- Stone, Ilana B.,Jermaks, Janis,MacMillan, Samantha N.,Lambert, Tristan H.
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supporting information
p. 12494 - 12498
(2018/09/18)
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- COMPOUND HAVING ALKENYL GROUP AT BOTH TERMINALS, LIQUID CRYSTAL COMPOSITION AND LIQUID CRYSTAL DISPLAY ELEMENT
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PROBLEM TO BE SOLVED: To provide a liquid crystalline compound satisfying at least one of demands for physical properties such as high stability to heat or light, a high clearing point (or a high maximum temperature), low minimum temperature of a liquid crystal phase, small viscosity, suitable optical anisotropy, large dielectric anisotropy, suitable elastic modulus and good compatibility with other liquid crystalline compounds, a liquid crystal composition comprising the above compound, and a liquid crystal display element containing the composition. SOLUTION: A compound represented by formula (1) is provided. In the formula, R1 and R2 each independently represent an alkenyl group having 2 to 10 carbon atoms, or the like; ring A1, ring A2 and ring A3 each independently represent 1,4-phenylene or 1-4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine; Z1 and Z2 each independently represent an alkylene having 1 to 4 carbon atoms, or the like and at least one of Z1 and Z2 may be a single bond; and a represents 1 or 2. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPO&INPIT
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Paragraph 0152
(2017/05/16)
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- Method for synthesis of acetal derivative by photocatalysis
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The invention discloses a method for synthesis of an acetal derivative by photocatalysis. The method consists of: in the presence of a photocatalyst, dissolving aldehyde and lower alcohol in an organic solvent, mixing the substances evenly, then carrying out reaction for 4-12h in an inert gas atmosphere and under a 300-600nm wavelength illumination condition, and then carrying out separation and purification, thus obtaining the acetal derivative. According to the invention, aldehyde, lower alcohol and the photocatalyst are employed to construct the acetal derivative by one step directly under room temperature illumination, the preparation method is simple, has mild conditions, and can prepare the target product high selectively; the raw materials are cheap and easily available, green and economical, also the method has very good substrate applicability, greatly expands the substrate range, and has very great application potential in biomedical synthetic intermediates.
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Paragraph 0035
(2017/04/19)
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- SPIROCYCLIC HAT INHIBITORS AND METHODS FOR THEIR USE
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Compounds having a structure of Formula (IX) or a stereoisomer, tautomer or pharmaceutically acceptable salt thereof, wherein R1, R2a, R2b, R3a, R3b, R4a, R4b, Q1----Q2, R6, R7, A, B, W, x, and y are as defined herein and are provided. Pharmaceutical compositions comprising such compounds and methods for treating various HAT-related conditions or diseases, including cancer, by administration of such compounds are also provided.
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Page/Page column 726
(2016/04/10)
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- Homochiral 2D Porous Covalent Organic Frameworks for Heterogeneous Asymmetric Catalysis
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There have been breakthroughs in the development of covalent organic frameworks (COFs) with tunability of composition, structure, and function, but the synthesis of chiral COFs remains a great challenge. Here we report the construction of two-dimensional
- Wang, Xiuren,Han, Xing,Zhang, Jie,Wu, Xiaowei,Liu, Yan,Cui, Yong
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supporting information
p. 12332 - 12335
(2016/10/07)
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- Palladium on Carbon-Catalyzed Chemoselective Oxygen Oxidation of Aromatic Acetals
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The development of an unprecedented chemoselective transformation has contributed to forming a novel synthetic process for target molecules. Chemoselective oxidation of aromatic acetals has been accomplished using a reusable palladium on carbon catalyst under atmospheric oxygen conditions to form ester derivatives with tolerance of aliphatic acetals and ketals.
- Yasukawa, Naoki,Asai, Shota,Kato, Maho,Monguchi, Yasunari,Sajiki, Hironao,Sawama, Yoshinari
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supporting information
p. 5604 - 5607
(2016/11/17)
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- Cyclopentyl methyl ether-NH4X: A novel solvent/catalyst system for low impact acetalization reactions
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Cyclopentyl methyl ether, a low impact ether forming a positive azeotrope with water, was successfully employed as a solvent in the synthesis of 1,3-dioxanes and 1,3-dioxolanes carried out under Dean-Stark conditions by the acetalization of aliphatic and aromatic aldehydes or ketones, employing ammonium salts as environmentally friendly acidic catalysts.
- Azzena, Ugo,Carraro, Massimo,Mamuye, Ashenafi Damtew,Murgia, Irene,Pisano, Luisa,Zedde, Giuseppe
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supporting information
p. 3281 - 3284
(2015/06/25)
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- Polyethyleneimine-Supported Triphenylphosphine and Its Use as a Highly Loaded Bifunctional Polymeric Reagent in Chromatography-Free One-Pot Wittig Reactions
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A polyethyleneimine-supported triphenylphosphine reagent has been synthesized and used as a highly loaded bifunctional homogeneous reagent in a range of one-pot Wittig reactions that afforded high yields of the desired products after simple purification procedures. The approach also served efficiently in tandem reaction sequences involving a one-pot Wittig reaction followed by conjugate reduction of the newly formed alkene product in situ. In these transformations, the phosphine oxide groups generated in the Wittig reaction served as the catalyst for activating trichlorosilane in the subsequent reduction reaction.
- Xia, Xuanshu,Toy, Patrick H.
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supporting information
p. 1737 - 1743
(2015/07/20)
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- Synthesis of polyfunctional secondary amines by the addition of functionalized zinc reagents to nitrosoarenes
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Addition of functionalized aryl, heteroaryl or adamantyl zinc reagents to various nitroso-arenes in the presence of magnesium salts and LiCl in THF produces after a reductive work-up with FeCl2 and NaBH4 in ethanol the corresponding polyfunctional secondary amines in high yields. This journal is
- Dhayalan, Vasudevan,S?mann, Christoph,Knochel, Paul
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p. 3239 - 3242
(2015/06/01)
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- Superaromatic terpyridines based on corannulene responsive to metal ions
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Two superaromatic terpyridine ligands (1 and 2) incorporating a corannulene unit at the 4′-position are reported. The optical and metal sensing properties of both ligands were investigated by the naked eye, and UV-vis and fluorescence spectroscopy in this work. In 1, the corannulene motif is directly connected to the 4′-phenylterpyridine domain, while in 2, the corannulene motif and the 4′-phenylterpyridine domain are separated by an acetylene linker. Both 1 and 2 can work as chemosensors for metal ions and display different optical responses to various metal ions. It is shown that both ligands exhibit a colorimetric sensing ability for Fe2+ through an obvious color change from colorless to magenta, and this color change can be observed easily by the naked eye. The addition of Fe2+ also leads to significant changes in the absorption spectra of the ligands. A characteristic red shift in the emission spectra is observed in the presence of Zn 2+, which facilitates the discrimination of Zn2+ from other metal ions. In addition, density functional theory (DFT) and time-dependent-density functional theory (TD-DFT) calculations were performed and shown to be consistent with the observed experimental results. The Royal Society of Chemistry.
- Wu, Difeng,Shao, Tao,Men, Jian,Chen, Xiaochuan,Gao, Guowei
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supporting information
p. 1753 - 1761
(2014/01/06)
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- Iron-catalyzed C-H bond functionalization for the exclusive synthesis of pyrido[1,2-a]indoles or triarylmethanols
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The efficient and selective iron-catalyzed C-H activation of 2-benzhydrylpyridine derivatives was employed for the preparation of pyrido[1,2-a]indoles through an intramolecular C-H amination reaction. In the presence of molecular oxygen as the sole oxidant, the same 2-benzhydrylpyridines were also used for the synthesis of the corresponding tertiary alcohols. In these approaches, the iron catalyst was used to selectively activate the C(sp2)-H bond of 2-benzhydrylpyridine, in the case of the intramolecular ring-closing C-H amination reaction in which the pyridine nitrogen atom was a directing group as well as a nucleophile, and the C(sp3)-H bond of the same compound, in the case of the oxidation reaction to give the corresponding triaryl carbinol.
- Karthikeyan, Iyyanar,Sekar, Govindasamy
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supporting information
p. 8055 - 8063
(2015/01/09)
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- Tandem catalysis by palladium nanoclusters encapsulated in metal-organic frameworks
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A bifunctional Zr-MOF catalyst containing palladium nanoclusters (NCs) has been developed. The formation of Pd NCs was confirmed by transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS). Combining the oxidation activity of Pd NCs and the acetalization activity of the Lewis acid sites in UiO-66-NH2, this catalyst (Pd@UiO-66-NH2) exhibits excellent catalytic activity and selectivity in a one-pot tandem oxidation-acetalization reaction. This catalyst shows 99.9% selectivity to benzaldehyde ethylene acetal in the tandem reaction of benzyl alcohol and ethylene glycol at 99.9% conversion of benzyl alcohol. We also examined various substituted benzyl alcohols and found that alcohols with electron-donating groups showed better conversion and selectivity compared to those with electron-withdrawing groups. We further proved that there was no leaching of active catalytic species during the reaction and the catalyst can be recycled at least five times without significant deactivation.
- Li, Xinle,Guo, Zhiyong,Xiao, Chaoxian,Goh, Tian Wei,Tesfagaber, Daniel,Huang, Wenyu
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p. 3490 - 3497
(2015/02/19)
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- A reversible fluorescence probe based on Se-BODIPY for the redox cycle between HClO oxidative stress and H2S repair in living cells
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We have developed a new reversible fluorescence probe MPhSe-BOD for the redox cycle process between hypochlorous acid and hydrogen sulfide in solution and in living cells. Confocal microscopy imaging using RAW264.7 cell lines shows that the probe has good
- Wang, Bingshuai,Li, Peng,Yu, Fabiao,Song, Ping,Sun, Xiaofei,Yang, Songqiu,Lou, Zhangrong,Han, Keli
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supporting information
p. 1014 - 1016
(2013/02/23)
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- A near-infrared reversible and ratiometric fluorescent probe based on Se-BODIPY for the redox cycle mediated by hypobromous acid and hydrogen sulfide in living cells
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We have developed a near-infrared (NIR) reversible and ratiometric fluorescence sensor based on Se-BODIPY for the redox cycle between hypobromous acid oxidative stress and hydrogen sulfide repair. Real-time imaging shows that the probe is able to monitor
- Wang, Bingshuai,Li, Peng,Yu, Fabiao,Chen, Junsheng,Qu, Zongjin,Han, Keli
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supporting information
p. 5790 - 5792
(2013/07/05)
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- Cyclic thiourea/urea functionalized triphenylamine-based dyes for high-performance dye-sensitized solar cells
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Six cyclic thiourea/urea functionalized triphenylamine-based dyes (AZ1-AZ6) containing 2-cyanoacrylic acid as an acceptor and various linkers (phenyl, biphenyl, and bithiophene) were synthesized. They exhibited high photovoltaic performance owing to an improved short-circuit photocurrent density (J sc) and open-circuit voltage (Voc). Among them, AZ6 bearing a cyclic thiourea group and bithiophene linker showed the highest power conversion efficiency (PCE) up to 7.29%, which was comparable to that of N719 (PCE = 7.36%).
- Wu, Zhisheng,An, Zhongwei,Chen, Xinbing,Chen, Pei
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supporting information
p. 1456 - 1459
(2013/07/05)
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- Homologative trifluoromethylation of acetals
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Trifluoroethyl α-insertion of acetals has been developed. Aromatic, heteroaromatic, and alkenyl acetals react with in situ generated (trifluoromethyl)diazomethane in the presence of antimony(V) chloride to furnish α-trifluoromethyl acetals. A stereoselective version of this transformation exploiting the acetal as a chiral auxiliary is also presented. Georg Thieme Verlag Stuttgart · New York.
- Hamilton, James Y.,Morandi, Bill,Carreira, Erick M.
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p. 1857 - 1862
(2013/07/26)
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- Orthogonal bis(terpyridine)-Fe(ii) metal complex oligomer wires on a tripodal scaffold: Rapid electron transport
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The present work reports a tripodal scaffold for bis(terpyridine)-Fe(ii) oligomer wires on an Au(111) surface: the tripodal scaffold realised both orthogonality of the oligomer wires, and fast interfacial electron transfer through the oligomer wires.
- Sakamoto, Ryota,Ohirabaru, Yuuki,Matsuoka, Ryota,Maeda, Hiroaki,Katagiri, Shunsuke,Nishihara, Hiroshi
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supporting information
p. 7108 - 7110
(2013/08/23)
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- Planar biphenyl-bridged biradicals as building blocks for the design of quantum magnets
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We have synthesized and investigated a new biphenyl-4,4′-bis(nitronyl nitroxide) radical with intermediately strong antiferromagnetic interactions. This organic biradical belongs to a family of materials that can be used as a building block for the design
- Mostovich, Evgeny A.,Borozdina, Yulia,Enkelmann, Volker,Removic-Langer, Katarina,Wolf, Bernd,Lang, Michael,Baumgarten, Martin
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scheme or table
p. 54 - 59
(2012/05/20)
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- Construction of soft porous crystal with silole derivative: Strategy of framework design, multiple structural transformability and mechanofluorochromism
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Novel fluorescent organic soft porous crystals have been designed and prepared based on a multi-substituted silole bearing 1-phenyl-2,2-dicyanoethene moieties (molecule 8). 8 exhibited a series of emission colors, ranging from yellow to dark red with an over 70 nm shift of emission maximum. Molecule 8 also showed the ability to reversibly switch between different solid states, and a typical mechanofluorochromism was observed by cyclic operation of the grinding-heating-cooling processes. In addition, two single crystals (O and R) were successfully obtained in proper conditions, and the crystallographic data indicated that crystal O and R had reasonable hollow structures, inside which different solvent molecules were selectively encapsulated. More importantly, we have presented a proof-of-concept example of the strategy for the designation of organic soft porous crystals with a conjugated fluorophore and demonstrated the successful achievement of softness, porosity and crystallization ability. This design strategy is instructive to design and construct organic soft porous crystals with other conjugated building blocks and develop novel smart and stimuli-responsive photo/electronic materials.
- Mei,Wang,Qin,Zhao,Yuan,Zhao,Sung,Deng,Zhang,Williams,Sun,Tang
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experimental part
p. 4290 - 4298
(2012/07/27)
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- Photochromic polymers bearing various diarylethene chromophores as the pendant: Synthesis, optical properties, and multicolor photochromism
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Photochromic polymers with various diarylethene derivatives were synthesized by a conventional radical polymerization of styrene derivatives having diarylethene chromophores as the pendant. All the polymers exhibited reversible photochromism in the film a
- Nishi, Hiroyasu,Namari, Tomoko,Kobatake, Seiya
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supporting information; experimental part
p. 17249 - 17258
(2012/05/04)
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- Synthesis and photovoltaic performances of donor-p-acceptor dyes utilizing 1,3,5-triazine as p spacers
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A series of new-type of donor-p-acceptor dyes (TCT-1-6) utilizing 1,3,5-triazine as p spacers were synthesized. These dyes were characterized by 1H NMR, ESI-MS, EA, and X-ray crystallography. Their photovoltaic performances were also investigat
- Liu, Jian,Wang, Kai,Xu, Feng,Tang, Zekun,Zheng, Wei,Zhang, Jiyuan,Li, Chenghui,Yu, Tao,You, Xiaozeng
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supporting information; experimental part
p. 6492 - 6496
(2011/12/16)
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- Acetalization of carbonyl compounds catalyzed by bismuth triflate under solvent-free conditions
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Carbonyl compounds were converted to the corresponding 1,3-dioxolanes and 1,3-dioxanes with ethylene glycol and 1,3-propandiol in the presence of bismuth triflate under solvent-free conditions. In addition, high chemoselective protection of aldehydes in the presence of ketones has been achieved.
- Aliyan, Hamid,Fazaeli, Razieh,Massah, Ahmad Reza,Momeni, Ahmad Reza,Naghash, Hamid Javaherian,Moeinifard, Behzad
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experimental part
p. 873 - 876
(2012/04/05)
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- Arene-ruthenium(II) complexes containing amino-phosphine ligands as catalysts for nitrile hydration reactions
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Three different series of novel mononuclear arene-ruthenium(II) complexes containing amino-phosphine ligands, namely, [RuCl2{κ 1(P)-2-Ph2PC6H4CH 2NHR}(η6-arene)], [RuCl2{κ 1(P)-3-Ph2PC6H4CH 2NHR}(η6-arene)], and [RuCl2{κ 1(P)-4-Ph2PC6H4CH 2NHR}(η6-arene)] (arene = C6H6, p-cymene, 1,3,5-C6H3Me3, C6Me 6; R = iPr, tBu; all combinations), have been synthesized and fully characterized. These readily accessible species are efficient catalysts for the selective hydration of organonitriles into amides under challenging reaction conditions, i.e., pure aqueous medium in the absence of any cocatalyst, being much more active than their corresponding nonfunctionalized triphenylphosphine counterparts [RuCl2(PPh 3)(η6-arene)]. The results obtained in this study indicate that the (amino-phosphine)ruthenium(II) complexes operate through a "bifunctional catalysis" mechanism in which the ruthenium center acts as a Lewis acid, activating the nitrile molecule, and the P-donor ligand acts as a Brnsted base, the pendant amino group generating the real nucleophile of the hydration process, i.e., the OH- group.
- Garcia-Alvarez, Rocio,Diez, Josefina,Crochet, Pascale,Cadierno, Victorio
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scheme or table
p. 3955 - 3965
(2010/12/25)
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- Energy transfer followed by electron transfer in a porphyrin macrocycle and central acceptor ligand: A model for a photosynthetic composite of the light-harvesting complex and reaction center
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A system that models a photosynthetic composite of the light-harvesting complex and reaction center is reported in which light energy collected by cyclic antenna porphyrins is transferred to a central energy-acceptor porphyrin, followed by photoinduced el
- Kuramochi, Yusuke,Sandanayaka, Atula S. D.,Satake, Akiharu,Araki, Yasuyuki,Ogawa, Kazuya,Ito, Osamu,Kobuke, Yoshiaki
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experimental part
p. 2317 - 2327
(2009/12/04)
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- NOVEL THERAPEUTIC COMPOUNDS
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Disclosed herein are novel compounds of Formula (I), wherein the variables are defined as herein. The compounds of Formula (I) are useful as kinase inhibitors and as such would be useful in treating certain conditions and diseases, especially inflammatory conditions and diseases as well as proliferative disorders such as cancer.
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Page/Page column 69
(2009/03/07)
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- Highly efficient and chemoselective acetalization of carbonyl compounds catalyzed by new and reusab e zirconyl triflate, zr0(0tf)2
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Various types of aromatic aldehydes were efficiently converted to their corresponding 1,3-dioxanes and 1,3-dioxolane with 1,3-propanediol and ethylene glycol, respectively, in the presence of catalytic amount of ZrO(OTf) 2 in acetonitrile at room temperature. The catalyst can be reused several times without loss of its catalytic activity. Very short reaction times, selective acetalization of aromatic aldehydes in the presence of aliphatic aldehydes and ketones, very mild reaction conditions, reusability of the catalyst, and easy workup are noteworthy advantages of this method.
- Moghadam, Majid,Mohammadpoor-Baltork, Iraj,Tangestaninejad, Shahram,Mirkhani, Valiollah,Yazdani, Parvin,Ghorjipoor, Saeedeh
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experimental part
p. 131 - 135
(2009/09/30)
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- Asymmetric synthesis of (S)-mirtazapine: Unexpected racemization through an aromatic ipso-attack mechanism
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An asymmetric synthesis of (S)-mirtazapine has been achieved from the synthesis of the racemate by using (S)-1-methyl-3-phenylpiperazine as the starting material. Unfortunately, significant racemization was encountered in the final step, which involved an electrophilic aromatic ring closure of a alcohol by concentrated sulfuric acid. A significantly higher ee was observed when polyphosphoric acid (PPA) was used instead. A remarkable correlation between the amount of PPA used and the ee of the product was revealed, namely, an increase in the ee upon decreasing the amount of PPA. This trend was paralleled by the formation of an increasing amount of a side-product upon lowering the amount of PPA. The racemization and formation of a side-product can be explained by an ipso-attack mechanism during the electrophilic aromatic ring-closure reaction. This mechanism was supported by a mechanistic study using a deuterium-labeled substrate. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Van Der Linden, Marco,Borsboom, Judith,Kaspersen, Frans,Kemperman, Gerjan
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experimental part
p. 2989 - 2997
(2009/04/07)
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- Intramolecular sensitization of photocleavage of the photolabile 2-(2-nitrophenyl)propoxycarbonyl (NPPOC) protecting group: Photoproducts and photokinetics of the release of nucleosides
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Novel photolabile protecting groups based on the 2-(2-nitrophenyl)- propoxycarbonyl (NPPOC) group with a covalently linked thioxanthone as an intramolecular triplet sensitizer exhibit significantly enhanced light sensitivity under continuous illumination. Herein we present a detailed study of the photokinetics and photoproducts of nucleosides caged with these new protecting groups. Relative to the parent NPPOC group, the light sensitivity of the new photolabile protecting groups is enhanced by up to a factor of 21 at 366 nm and is still quite high at 405 nm, the wavelength at which the sensitivity of the parent compound is practically zero. A new pathway for de-protection of the NPPOC group pro_ceeding through a nitroso benzylalcohol intermediate has been discovered to complement the main mechanism, which involves β elimination. Under standard conditions of lithographic DNA-chip synthesis, some of the new compounds, while maintaining the same chip quality, react ten times faster than the unmodified NPPOC-protected nucleosides.
- Woell, Dominik,Smirnova, Julia,Galetskaya, Marina,Prykota, Tamara,Buehler, Jochen,Stengele, Klaus-Peter,Pfleiderer, Wolfgang,Steiner, Ulrich E.
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supporting information; experimental part
p. 6490 - 6497
(2009/09/06)
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- Protection and deprotection of acetals by using MoO3/SiO 2
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Acetalization of aldehydes using a new silica-supported molybdenum(VI) oxide (20%) catalyst has been explored. Additionally, facile deprotection strategy for the acetals is reported including the results from the replacement of solvent studies. The protocol achieved the protection O,O-acetals in excellent yield within a few hours under neutral conditions and also deprotection of aromatic O,O-acetals in excellent yields was achieved within a few minutes in aqueous acetone. Copyright Taylor & Francis Group, LLC.
- Bhosale, Rajesh S.,Bhosale, Sidhanath V.,Bhosale, Sheshanath V.,Solanke, Kuldeep S.,Pawar, Rajendra P.,Chougule, Harish S.,Dongare, Mohan K.
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p. 659 - 663
(2007/10/03)
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- A new approach to combretastatin D2
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A concise and convergent route to combretastatin D2 is described together with some preliminary biological data. The Royal Society of Chemistry 2006.
- Cousin, David,Mann, John,Nieuwenhuyzen, Mark,Van Den Berg, Hendrik
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- Synthesis and binding affinities of methylvesamicol analogs for the acetylcholine transporter and sigma receptor
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We synthesized methylvesamicol analogs 13-16 and investigated the binding characteristics of 2-[4-phenylpiperidino]cyclohexanol (vesamicol) and methylvesamicol analogs 13-16, with a methyl group introduced into the 4-phenylpiperidine moiety, to sigma receptors (σ-1, σ-2) and to vesicular acetylcholine transporters (VAChT) in membranes of the rat brain and liver. In competitive inhibition studies, (-)-o-methylvesamicol [(-)-OMV] (13) (Ki = 6.7 nM), as well as (-)-vesamicol (Ki = 4.4 nM), had a high affinity for VAChT. (+)-p-Methylvesamicol [(+)-PMV] (16) (Ki = 3.0 nM), as well as SA4503 (Ki = 4.4 nM), reported as a σ-1 mapping agent for positron emission tomography (PET), had a high affinity for the σ-1 receptor. The binding affinity of (+)-PMV (16) for the σ-1 receptor (Ki = 3.0 nM) was about 13 times higher than that for the sigma-2 (σ-2) receptor (Ki = 40.7 nM). (+)-PMV (16) (K i = 199 nM) had a much lower affinity for VAChT than SA4503 (K i = 50.2 nM) and haloperidol (Ki = 41.4 nM). These results showed that the binding characteristics of (-)-OMV (13) to VAChT were similar to those of (-)-vesamicol and that (+)-PMV (16) bound to the σ-1 receptor with high affinity. In conclusion, (-)-OMV (13) and (+)-PMV (16), which had a suitable structure, with a methyl group for labeling with 11C, may become not only a new VAChT ligand and a new type of σ receptor ligand, respectively, but may also become a new target compound of VAChT and the σ-1 receptor radioligand for PET, respectively.
- Shiba, Kazuhiro,Ogawa, Kazuma,Ishiwata, Kiichi,Yajima, Kazuyoshi,Mori, Hirofumi
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p. 2620 - 2626
(2007/10/03)
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