- A Metal–Organic Supramolecular Box as a Universal Reservoir of UV, WL, and NIR Light for Long-Persistent Luminescence
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Long persistent luminescence (LPL) materials have a unique photophysical mechanism to store light radiation energy for subsequent release. However, in comparison to the common UV source, white-light (WL) and near-infrared (NIR) excited LPL is scarce. Herein we report a metal–organic supramolecular box based on a D–π–A-type ligand. Owing to the integrated one-photon absorption (OPA) and two-photon absorption (TPA) attributes of the ligand, the heavy-atom effect of the metal center, as well as π-stacking and J-aggregation states in the supramolecular assembly, LPL can be triggered by all wavebands from the UV to the NIR region. This novel designed supramolecular kit to afford LPL by both OPA and TPA pathways provides potential applications in anti-counterfeiting, camouflaging, decorating, and displaying, among others.
- Wang, Zheng,Zhu, Cheng-Yi,Yin, Shao-Yun,Wei, Zhang-Wen,Zhang, Jian-Hua,Fan, Ya-Nan,Jiang, Ji-Jun,Pan, Mei,Su, Cheng-Yong
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Read Online
- Orthogonal insertion of lanthanide and transition-metal atoms in metal-organic networks on surfaces
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The orthogonal coordinative properties of tetrapyrrole macrocycles and nitrile ligands have been used in a multistep procedure towards interfacial d-f hetero-bimetallic nanoarchitectures based on a free-base porphyrin derivative functionalized with meso-c
- Urgel, José I.,Ecija, David,Auw?rter, Willi,Stassen, Daphné,Bonifazi, Davide,Barth, Johannes V.
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Read Online
- Pd(II)-Metalated and l-Proline-Decorated Multivariate UiO-67 as Bifunctional Catalyst for Asymmetric Sequential Reactions
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The construction of a multifunctional catalyst for multistep sequentialtandem reactions at the molecular level faces a formidable challenge. Multivariate (MTV)-MOFs can provide a facile and tunable platform for rationally designing such multifunctional catalysts via grafting different catalytic groups on the bridging ligands. However, the related investigations are still limited. Here, Pd(II) and l-proline are metalated and decorated to organic linkers, respectively, to build a MTV-MOF, which is then successfully applied to sequential Suzuki Coupling/asymmetric Aldol reactions with satisfied coupling performance (yields up to 99%) and good enantioselectivities (eeanti up to 98%). Inductively coupled plasma optical emission spectrometer (ICP-OES) measurements of the supernatant and hot leaching test suggest the heterogeneous nature of the catalyst. Macrosubstrate tests verify that the reaction occurs inside the pores of the MOF. The heterogeneous catalyst can maintain structural stability and catalytic activity within three cycles. Graphic Abstract: Versatile Pd(II) and l-proline were metalated and decorated, respectively, into stable UiO-67 to construct bifunctional and heterogeneous multivariate MOF catalyst, which displayed efficient and recyclable catalytic activity in sequential Suzuki Coupling/asymmetric Aldol reactions.[Figure not available: see fulltext.]
- Cheng, Lin,Cao, Liumei,Ren, Hao,Guo, Qiaoqiao,Deng, Huifang,Li, Yiming
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p. 1160 - 1169
(2021/07/06)
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- Structure-Activity Relationship and Mode-Of-Action Studies Highlight 1-(4-Biphenylylmethyl)-1H-imidazole-Derived Small Molecules as Potent CYP121 Inhibitors
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CYP121 of Mycobacterium tuberculosis (Mtb) is an essential target for the development of novel potent drugs against tuberculosis (TB). Besides known antifungal azoles, further compounds of the azole class were recently identified as CYP121 inhibitors with
- Walter, Isabell,Adam, Sebastian,Gentilini, Maria Virginia,Kany, Andreas M.,Brengel, Christian,Thomann, Andreas,Sparwasser, Tim,K?hnke, Jesko,Hartmann, Rolf W.
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supporting information
p. 2786 - 2801
(2021/06/27)
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- Method for synthesizing biphenyl compound by taking suaeda salsa extract liquor as solvent
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The invention discloses a method for synthesizing a biphenyl compound by using suaeda salsa extract as a solvent in the technical field of organic chemical synthesis, which comprises the following steps: roasting suaeda salsa in a muffle furnace to obtain ash, dissolving the ash in distilled water, refluxing, cooling the solution, and filtering to obtain a faint yellow solution which is the suaedasalsa extract liquor; sequentially adding 1mmol of aryl halide, 1.1mmol of arylboronic acid, 0.001mmol to 0.01mmol of a catalyst and 4ml of the suaeda salsa extract liquor into a round-bottom flask,stirring at 100 DEG C to react for 2 hours, cooling the reactant to room temperature, filtering, mixing the obtained filter residue with a palladium catalyst to obtain a mixture; and dissolving the mixture in ethyl acetate, filtering to remove the palladium catalyst, and drying the filtrate by distillation to obtain the biphenyl compound. According to the scheme, a phosphine ligand, alkali and anadditive do not need to be added, a Suzuki reaction system with biomass extract as a reaction medium is adopted, and a green, simple, convenient and efficient method is provided for synthesizing biphenyl compounds.
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Paragraph 0059-0060
(2020/06/30)
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- Method for synthesizing biphenyl compound by taking phenol as raw material
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The invention discloses a method for synthesizing a biphenyl compound by using phenol as a raw material in the technical field of organic chemical synthesis, which comprises the following steps: carrying out a mixed reaction process on phenol or substituted phenol, alkali and 50-90% ethanol aqueous solution, slowly introducing sulfonyl fluoride gas, and carrying out magnetic stirring reaction at normal temperature for 4-12 hours, adding arylboronic acid, alkali and a palladium catalyst into a round-bottom flask, continuing to react for 6-12 hours at normal temperature, after the reaction is finished, adding a saturated edible salt solution into the round-bottom flask, carrying out a water quenching reaction process to obtain a reaction mixture, extracting a reaction product from the reaction mixture by using ethyl acetate, combining organic phases, concentrating filtrate, and separating the concentrated filtrate by using column chromatography to obtain analytically pure biphenyl or terphenyl compounds. By using the method, on one hand, the production cost of the biphenyl compound is reduced, and on the other hand, the method also has a wide application prospect in the aspects of synthesis of natural products, medicines, pesticides, herbicides, polymer conduction materials, liquid crystal materials and the like.
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Paragraph 0086-0088
(2020/07/15)
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- Chiral Proline-Decorated Bifunctional Pd?NH2-UiO-66 Catalysts for Efficient Sequential Suzuki Coupling/Asymmetric Aldol Reactions
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The design and development of site-isolating and multifunctional catalysts for multistep sequential reactions at the molecular level is a significant challenge. Herein, we first report bifunctional metal NPs?chiral MOFs catalysts for asymmetric sequential reactions. Pd nanoparticles and chiral proline were successfully added to NH2-UiO-66 to construct two chiral bifunctional catalysts, in which active Pd nanoparticles were encapsulated into the frameworks via the "bottle-around-ship" method, and chiral proline was introduced into NH2-UiO-66 by coordination to zirconium nodes and postsynthetic modification (PSM) of the organic linkers. The chiral proline-decorated bifunctional Pd?NH2-UiO-66 catalysts were applied to sequential Suzuki coupling/asymmetric aldol reactions with excellent coupling performance (yields up to 99.9%) and good enantioselectivities (eeanti values up to 97%). The heterogeneous catalyst by coordination of proline can be reused, and the reaction activity was not significantly reduced after four cycles.
- Chen, Jinxi,Cheng, Lin,Li, Yiming,Lou, Yongbing,Zhai, Qingchao,Zhang, Qingsong,Zhao, Kaiyuan
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- Monosubstituted, Anionic Imidazolyl Ligands from N?H NHC Precursors and Their Activity in Pd-Catalyzed Cross-Coupling Reactions
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We report that treatment of several 2-diphenylphosphinoimidazoles with Pd(II) salts generates monosubstituted N?H NHC?Pd complexes via insertion into the C?P bond. Removal of the N?H proton in situ leads to anionic (X-type) or imidazolyl-Pd complexes that are highly stable and catalytically active, achieving up to 340,000 turnovers at 1 ppm catalyst loading in Suzuki-Miyaura reactions. DFT-calculated Tolman electronic parameters for the sterically small ligands suggest that these ligands are significantly more donating than traditional NHCs, which provides a rationale for rapid cross-coupling catalysis. Excellent reactivity is also demonstrated in Sonogashira reactions. (Figure presented.).
- Clark, Kyle J.,Ess, Daniel H.,Jensen, Christopher A.,Kenney, Karissa C.,Larson, Alexandra J. S.,Martinez, Erin E.,Michaelis, David J.,Nazari, S. Hadi,Smith, Stacey J.,Valdivia-Berroeta, Gabriel A.
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supporting information
(2020/07/06)
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- Conjugated Macrocycle Polymer Nanoparticles with Alternating Pillarenes and Porphyrins as Struts and Cyclic Nodes
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Conjugated macrocycle polymers (CMPs) integrated using the macrocyclic confinement effect make imposing restrictions feasible on the growth of metal nanoparticles with confined size and high dispersion. For a proof-of-concept exploration, a novel nanoscale CMP is reported, denoted as DMP[5]-TPP-CMP, comprising two representative types of macrocyclic compounds, i.e., pillararene and porphyrin, as alternating strut/node components in the skeleton. With abundant anchoring sites, CMP implanted with Pd nanoparticles (Pd@DMP[5]-TPP-CMP, Pd@CMP for short) is successfully obtained through a simple post-treatment, exhibiting remarkable catalytic activity in Suzuki–Miyaura coupling (SMC) and nitrophenol reduction. The as-prepared Pd@CMP material shows favorable performance in expediting the process of SMC with an appreciable yield even under mild conditions, as well as in facilitating the electron transfer process from borohydride to nitrophenol through metal–hydride complex to produce aminophenol with a very short transformation time of 3 min and superior apparent kinetic rate constant k app of 1.9 × 10?2 s?1, higher than most palladium supports. Significantly, this multifunctional Pd@CMP composite material not only enriches the family of CMPs, but also sheds light on the development of green catalysts with excellent stability and easy recyclability without deactivation.
- Li, Zheng,Li, Xi,Yang, Ying-Wei
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- Copper-Free Click Reaction Sequence: A Chemoselective Layer-by-Layer Approach
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An additive-free chemoselective ligation of dual clickable building blocks is demonstrated. The challenge of balancing reactivity and stability was achieved by employing a small, electron-deficient tetrazine bearing an azido group and an enol ether functionalized cyclooctyne. The chemoselective sequence of strain-promoted azide-alkyne cycloaddition (SPAAC) and inverse-electron-demand Diels-Alder (IEDDA) reaction is demonstrated with a cholic acid derived triazide as a molecular surface model for layer-by-layer synthesis.
- Meinecke, Jannick,Koert, Ulrich
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supporting information
p. 7609 - 7612
(2019/10/02)
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- Palladium-Catalyzed Late-Stage Direct Arene Cyanation
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Methods for direct benzonitrile synthesis are sparse, despite the versatility of cyano groups in organic synthesis and the importance of benzonitriles for the dye, agrochemical, and pharmaceutical industries. We report the first general late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance. The reaction is enabled by a dual-ligand combination of quinoxaline and an amino acid-derived ligand. The method is applicable to direct cyanation of several marketed small-molecule drugs, common pharmacophores, and organic dyes. Benzonitriles are some of the most versatile building blocks for organic synthesis, in particular in the pharmaceutical industry, but general methods to make them by direct C–H functionalization are unknown. In this issue of Chem, Ritter and coworkers describe a late-stage aryl C–H cyanation with broad substrate scope and functional-group tolerance, enabled by a palladium-dual-ligand catalyst system. The reaction may serve for the late-stage modification of drug candidates. Aryl nitriles constitute an important class of organic compounds that are widely found in natural products, pharmaceuticals, agricultural chemicals, dyes, and materials. Moreover, nitriles are versatile building blocks to access numerous other important molecular structure groups. However, no general method for direct aromatic C–H cyanation is known. All approaches to date require either an appropriate directing group or reactive electron-rich substrates, such as indoles, which limit their synthetic applications. Here we describe an undirected, palladium-catalyzed late-stage aryl C–H cyanation reaction for the synthesis of complex aryl nitriles that would otherwise be more challenging to produce. The wide substrate scope and good functional-group tolerance of this reaction provide direct and quick access to structural diversity for pharmaceutical and agrochemical development.
- Zhao, Da,Xu, Peng,Ritter, Tobias
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supporting information
p. 97 - 107
(2019/01/21)
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- Sterically hindered N-aryl/benzyl substituted piperidoimidazolin-2-ylidene palladium complexes and their catalytic activities
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A series of N-aryl (2a,b) or benzyl (2c,d) substituted piperidoimidazolinium salts and their palladium complexes (3a-d) were prepared and characterized by 1H, 13C NMR, IR spectroscopy and elemental analysis. The crystal structures of 3a and 3c have been determined by X-ray crystallography. Thermogravimetric analysis (TGA) was applied to complexes (3a–d). The palladium complexes have been employed as catalyst for Suzuki-Miyaura cross coupling. The N-aryl substituted complex 3b was a highly efficient precatalyst and successfully employed in Suzuki-Miyaura cross coupling reactions of (hetero)aryl chlorides with arylboronic acids in air. In addition, the oxidative addition step of the reaction mechanism involving chlorobenzene and the catalysts 3a, 3b, 3c and 3d were computationally investigated by the DFT-ω-B97X-D method and complete agreement were obtained with the catalytic results. To measure σ-donating and π-acceptor properties of the new ligands, the rhodium carbonyl complexes were also prepared.
- Gacal, Elif,Denizalt?, Serpil,K?nal, Arma?an,G?k?e, Ayta? Gürhan,Türkmen, Hayati
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p. 6829 - 6838
(2018/10/20)
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- Bench-Stable Sulfoxide-Based Boronates: Preparation and Application in a Tandem Suzuki Reaction
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A set of novel aromatic and heteroaromatic bench-stable sulfoxide-based boronates was prepared. The structure of the boronates was established by means of X-ray crystallography, and the prepared boronates were successively used in Suzuki cross-coupling reactions under different conditions. We also developed a tandem Suzuki reaction so that a base is generated during the nucleophilic addition of Grignard reagents to 4-bromobenzaldehyde. The formed intermediates were smoothly coupled with the prepared boronates and the boronic acids under external base-free conditions. (Figure presented.).
- ?ubiňák, Marek,Eigner, Václav,Tobrman, Tomá?
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p. 4604 - 4614
(2018/10/31)
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- Insights into the Catalytic Activity of [Pd(NHC)(cin)Cl] (NHC=IPr, IPrCl, IPrBr) Complexes in the Suzuki–Miyaura Reaction
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The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki–Miyaura reaction were investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands (IPr=1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene; cin=cinnamyl) were synthesized. After determining the electronic and steric properties of these ligands, their properties were compared to those of [Pd(IPr) (cin)Cl]. The three palladium complexes were studied by using DFT calculations to delineate their behavior in the activation step leading to the putative 12-electron active catalyst. Experimentally, their catalytic activity in the Suzuki–Miyaura reaction involving a wide range of coupling partners (30 entries) at low catalyst loading was studied.
- Izquierdo, Frédéric,Zinser, Caroline,Minenkov, Yury,Cordes, David B.,Slawin, Alexandra M. Z.,Cavallo, Luigi,Nahra, Fady,Cazin, Catherine S. J.,Nolan, Steven P.
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p. 601 - 611
(2017/12/26)
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- Development of benzylidene-methyloxazolone based AIEgens and decipherment of their working mechanism
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Based on an analogue of green fluorescent protein chromophore benzylidene-methyloxazolone (BMO), a series of fluorophores with an additional phenyl group, BMO-PH, BMO-PF, BMO-PM and BMO-PC, have been prepared and are found to be AIE-active. Their solutions are weakly emissive and their aggregation or solid states are highly emissive. Although these compounds readily undergo efficient E/Z isomerization (EZI) upon UV irradiation in solution, the intramolecular rotation around the double bond and phenyl rotation around the single bond serve as the key non-radiative decay channels to dissipate the excited-state energies. The EZI is only the phenomenal result. In aggregates, these intramolecular motions are greatly restricted by multiple intermolecular interactions, resulting in the AIE effect. To ensure a high solid-state quantum yield, prevention of detrimental π-π stacking is of essence. An additional phenyl group to BMO is found to increase the π-π distance and weaken the π-π interaction. Thus, the quantum yields are increased. Strong electron-donating groups and extended conjugation are effective at tuning the emission color bathochromically. Based on these principles, we succeeded in increasing the solid-state quantum yield up to 50% and obtaining a red emission maximum of 635 nm. Moreover, these compounds are promising for applications in photoswitches and fluorescent patterns, and their crystals are good candidates for luminescent waveguides with low light loss efficiency.
- Jiang, Meijuan,He, Zikai,Zhang, Yilin,Sung, Herman H. Y.,Lam, Jacky W. Y.,Peng, Qian,Yan, Yongli,Wong, Kam Sing,Williams, Ian D.,Zhao, Yongsheng,Tang, Ben Zhong
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supporting information
p. 7191 - 7199
(2017/08/04)
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- Tailoring Large Pores of Porphyrin Networks on Ag(111) by Metal–Organic Coordination
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The engineering of nanoarchitectures to achieve tailored properties relevant for macroscopic devices is a key motivation of organometallic surface science. To this end, understanding the role of molecular functionalities in structure formation and adatom
- Bischoff, Felix,He, Yuanqin,Seufert, Knud,Stassen, Daphné,Bonifazi, Davide,Barth, Johannes V.,Auw?rter, Willi
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supporting information
p. 15298 - 15306
(2016/10/13)
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- Towards understanding the NTB phase: A combined experimental, computational and spectroscopic study
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Today liquid-crystalline materials are most widely exploited for flat-panel displays, and yet their ability to self-organize into periodically ordered nanostructures gives rise to a broad variety of additional applications. The recently discovered low-temperature nematic phase (NTB) with unusual characteristics generated considerable attention within the scientific community: despite the fact that the molecules from which the phase is composed are not chiral, the helicoidal structure of the phase is strongly implicated. Here we present a combined experimental, computational and spectroscopic study of the structural aspects influencing the formation of the NTB phase as well as the possible molecular organization within the phase. In an extensive DFT study, the structure-property prerequisite was traced to a bent-propeller shape of the molecule. Computational analysis of two possible types of molecular packing suggests that the syn-arrangement of dimeric molecules is energetically more favorable than the anti-arrangement. The NOESY investigation in the isotropic melt just prior to the Iso-N transition shows the presence of intermolecular interactions that can be attributed to the syn-parallel orientation of the mesogens. The synergy of experimental, computational and NMR studies provides a new insight into possible molecular organization within the NTB phase, supporting the hierarchical model in which self-assembly of dimeric molecules with syn-parallel orientation formed in the isotropic melt represents the nucleus for its complex helical superstructures in the NTB phase.
- Iv?i?, Trpimir,Vinkovi?, Marijana,Baumeister, Ute,Mikleu?evi?, Ana,Lesac, Andreja
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p. 5000 - 5007
(2016/01/29)
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- Milestone in the NTB phase investigation and beyond: Direct insight into molecular self-assembly
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Although liquid-crystalline materials are most widely exploited for flat-panel displays, their ability to self-organize into periodically ordered nanostructures gives rise to a broad variety of additional applications. The recently discovered low-temperature nematic phase (NTB) with unusual characteristics generated considerable attention within the scientific community: despite the fact that the molecules from which the phase is composed are not chiral, the helicoidal structure of the phase is strongly implicated. Here we report on combined experimental, computational and spectroscopic studies of the structural aspects influencing formation of the NTB phase as well as on the molecular organization within the phase. In an extensive DFT study, the structure-property prerequisite was traced to a bent-propeller shape of the molecule. We also demonstrate the first utilization of liquid state NMR for direct analysis of intermolecular interactions within thermotropic liquid-crystalline phases, providing new insight into molecular packing that can lead towards design of novel chiral functional materials. The synergy of experimental, computational and NMR studies suggests a syn-parallel helical molecular organization within the NTB phase. This journal is
- Ivi, Trpimir,Vinkovi, Marijana,Baumeister, Ute,Mikleuevi, Ana,Lesac, Andreja
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p. 9334 - 9342
(2015/02/19)
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- Photodynamics of [26]- and [28]hexaphyrin-bodipy hybrids
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A set of hybrids having gradual variation in distances between hexaphyrin and bodipy moieties, given by uses of phenylene, biphenylene, and triphenyelene bridges was prepared. Efficient PET processes from bodipy (donor) to [26]- or [28]hexaphyrin (acceptor) were successfully observed, where the PET speed was controlled by intramolecular distances between the donor and the acceptor. UV irradiation at 515 nm raised a band corresponding to the bodipy absorption. As the time delayed, the bodipy bands decreased and new absorption bands at 615 and 580 nm corresponding to respective absorption bands of [28]- and [26]-hybrids gradually appeared. Whereas the femtosecond transient absorption spectra of [28]/[26]-hybrids having terphenylene bridges completely showed energy transfers from bodipy to hexaphyrin, irradiation of the hybrids using 615 and 580 nm pulses did not induce opposite ways of the PET process. On the basis of enlarged center-to-center-distances of [26]-hybrids than those of [28]-hybrids, the set of [26]-hybrids resulted in slow decay/rise processes. PET parameters obtained with the experiments were fairly consistent with the PET parameters calculated. Speed control: A set of hybrids having gradual variation in distances between hexaphyrin and bodipy moieties was prepared (see figure). Efficient PET processes from bodipy to [26]/[28]hexaphyrin were successfully observed on terphenylene-containing hybrids. [26]-Hybrids performed slower speeds of decay/rise processes than [28]-hybrids on the basis of enlarged center-to-center distances.
- Shin, Ji-Young,Kim, Kilsuk,Lim, Jong Min,Tanaka, Takayuki,Kim, Dongho,Kim, Kimoon,Shinokubo, Hiroshi,Osuka, Atsuhiro
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supporting information
p. 4574 - 4582
(2014/05/06)
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- Benzimidazole-based palladium-N-heterocyclic carbene: A useful catalyst for C-C cross-coupling reaction at ambient condition
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A convenient way for the synthesis of benzimidazole-based Pd-N-heterocyclic carbene complex and its structural characterization are described. The complex efficiently catalyzes Suzuki cross-coupling reaction in a wide variety of substrates including heteroaromatic system at ambient condition. The catalyst is also effective for multi Suzuki cross-coupling reaction. In addition, the catalyst is equally active toward C-C cross-coupling reaction between acid chloride and arylboronic acid, giving the desired ketones in high yield.
- Gupta, Sumanta,Basu, Basudeb,Das, Sajal
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p. 122 - 128
(2013/01/15)
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- Flow synthesis of arylboronic esters bearing electrophilic functional groups and space integration with Suzuki-Miyaura coupling without intentionally added base
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We found that an integrated flow microreactor system enables the preparation of boronic esters bearing electrophilic functional groups using organolithium chemistry and that it allows for their use in Suzuki-Miyaura cross-coupling without intentionally added base. Based on this method, cross-coupling of two aryl halides bearing electrophilic functional groups was accomplished to obtain the corresponding biaryl compounds in one flow.
- Nagaki, Aiichiro,Moriwaki, Yuya,Yoshida, Jun-Ichi
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supporting information
p. 11211 - 11213
(2013/01/15)
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- Sequential Suzuki/asymmetric aldol and Suzuki/Knoevenagel reactions under aqueous conditions
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Here we describe for the first time a sequential Suzuki/asymmetric aldol reaction. Such sequential approach was achieved through the combined use of an ionic liquid supported palladium catalyst and the organocatalyst trans-4-(2,2-diphenylacetoxy)proline. Suzuki and asymmetric aldol reactions were performed under aqueous conditions. The use of a palladium catalyst under basic conditions allowed also the first example of sequential Suzuki/Knoevenagel reaction. Reactions were carried out under aqueous conditions and products were isolated in good to high yields and, in the case of the Suzuki/aldol reaction, with diastereoselectivities up to 91:9 and enantioselectivities up to at least 99%.
- Gruttadauria, Michelangelo,Bivona, Lucia Anna,Lo Meo, Paolo,Riela, Serena,Noto, Renato
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experimental part
p. 2635 - 2642
(2012/06/04)
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- Imidazole as a central π-linkage in Y-shaped push-pull chromophores
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Twelve imidazole based Y-shaped push-pull chromophores have been designed, synthesised and fully characterised featuring 4,5-bis(N,N-dimethylanilino) imidazole as a donor moiety, a systematically enlarged π-linker and nitro and cyano groups as acceptors.
- Kulhánek, Ji?í,Bure?, Filip,Mikysek, Tomá?,Ludvík, Ji?í,Pytela, Old?ich
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scheme or table
p. 48 - 55
(2011/12/04)
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- Highly practical boronic acid surrogates for the Suzuki-Miyaura cross-coupling
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Boronic acids and esters are well known substrates for the Suzuki-Miyaura cross-coupling. Yet their isolation can sometimes be tedious. We report here that the use of aryl dioxazaborocanes afford a simple isolation procedure while keeping a high efficienc
- Bonin, Hélne,Leuma-Yona, Rodrigue,Marchiori, Bruno,Demonchaux, Patrice,Gras, Emmanuel
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p. 1132 - 1135
(2011/03/22)
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- THIAZOLE COMPOUNDS AS ACTIVATORS OF SOLUBLE GUANYLATE CYCLASE
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Disclosed are compounds of formula (I) wherein R1 and R2 are independently selected from hydrogen, halo, C1-4alkyl, C1-4alkoxy, CF3 and OCF3; -Y- represents formula (IA) R3 represents hydrogen, fluoro, chloro or C1-4alkyl; R4a and R4b each independently represent hydrogen, C1-4alkyl, C1-4alkoxy, CF3 or halo; and R5 represents a group Z-X; wherein Z is absent or represents (CH2)2 or O; and X represents formula (IB) wherein: J and L both represent CH, or one of J and L represents CH and the other represents N; when both J and L represent CH, R6 represents hydrogen, halo, CF3, C1-4alkyl or C1-4alkoxy in a meta or ortho position relative to the R7 substituent and R7 represents hydrogen, halo, CF3, OCF3, C1-4alkyl, C1-4alkoxy, CH2OH, CN, CONR8R9 or CO2H; or when one of J or L represents N, R6 represents hydrogen or halo in a meta or ortho position relative to the R7 substituent and R7 represents hydrogen, halo, CF3, C1-4alkyl, C1-4alkoxy, CH2OH, CN, CONR8R9 or CO2H; and R8 and R9 are independently selected from hydrogen and C1-4alkyl; or salts thereof which activate soluble guanylate cyclase (sGC), pharmaceutical compositions containing them, their use in medicine, and processes for their preparation.
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Page/Page column 45-46
(2010/04/03)
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- PYRIMIDINE DERIVATIVES AS ACTIVATORS OF SOLUBLE GUANYLATE CYCLASE
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Disclosed are compounds of formula (I) and or salts thereof which activate soluble guanylate cyclase (sGC), pharmaceutical compositions containing them, their use in the manufacture of a medicament for teating cardiovascular diseases, and processes for their preparation.
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Page/Page column 36
(2010/04/03)
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- 2,6-DISUBSTITUTED PYRIDINES AS SOLUBLE GUANYLATE CYCLASE ACTIVATORS
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Disclosed are compounds of formula (I) wherein R1 and R2 are independently selected from hydrogen, halo, CF3, C1-4alkyl and allyl; Y represents (II), (III), (IV) or (V) wherein R3 represents CF3 or C1-4alkyl; and R3a represents CF3 or C1-4alkyl.
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Page/Page column 58
(2009/07/17)
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- New and efficient arrays for photoinduced charge separation based on perylene bisimide and corroles
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The bichromophoric systems C2-PI, C3-PI, and C3-PPI consisiting of corrole and perylene bisimide units and representing one of the rare cases of elaborate structures based on corrole, have been synthesized. Corroles C2 and C3 are, respectively, meso-substituted corroles with 2,6-dichlorophenyl and pentafluorophenyl substituents at the 5 and 15 positions. The three dyads were prepared by divergent strategy with the corrole-forming reaction as the last step of the sequence. C2-PI and C3-PI differ in the nature of the corroles, whereas C3-PI differs from C3-PPI in the presence of a further phenyl unit in the linker between photoactive units. The dyads display spectroscopic properties which are the superposition of the component spectra, indicating a very weak electronic coupling. Excitation of the corrole unit leads to charge separation with a rate which decreases from 2.4 × 1010, to 5.0 × 109, and to 4.9 × 107 s-1 for C2-PI, C3-PI, and C3-PPI, respectively, where the reaction is characterized by a ΔG° > 0. Excitation of the perylene bisimide unit is followed by competing reactions of; 1) energy transfer to the corrole unit, which subsequently deactivates to the charge-separated state and; 2) electron transfer to directly form the charge-separated state. The ratio of electron-to-energy- transfer rates is 9;1 and 1;1 for C3-PI and C3-PPI, respectively. The yield of charge separation is essentially 100% for C2-PI and C3-PI, and approximately 50% (excitation of peryleneimide) or 15% (excitation of the corrole) for C3-PPI. The lifetime of the charge-separated state, observed for the first time in corrole-based structures, is 540 ps for C2-PI, 2.5 ns for C3-PI, and 24 ns for C3-PPI, respectively. This is in agreement with an inverted behavior, according to Marcus theory.
- Flamigni, Lucia,Ventura, Barbara,Tasior, Mariusz,Becherer, Thomas,Langhals, Heinz,Gryko, Daniel T.
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p. 169 - 183
(2008/09/18)
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- Suzuki-Miyaura coupling reaction of aryl chlorides using di(2,6-dimethylmorpholino)phenylphosphine as ligand
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Suzuki-Miyaura coupling was achieved on a variety of aryl chlorides by using di(2,6-dimethylmorpholino)phenylphosphine (L1) as a bulky electron-rich monoaryl phosphine ligand. We report the couplings of various chlorobenzenes and heteroaryl chlorides.
- Cho, Su-Dong,Kim, Ho-Kyun,Yim, Heung-seop,Kim, Mi-Ra,Lee, Jin-Kook,Kim, Jeum-Jong,Yoon, Yong-Jin
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p. 1345 - 1352
(2007/10/03)
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- The fluorescence labelling of primary amines with perylenetetracarboxdiimides
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The synthesis of perylenetetracarboxdiimide-labelled aldehydes is described as well as their condensation with primary amines. Thus, a highly fluorescent and light-fast fluorescence labelling process has been demonstrated. Application of this method to bi
- Langhals, Heinz,Becherer, Thomas,Lindner, Joerg,Obermeier, Andreas
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p. 4328 - 4336
(2008/04/13)
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- Direct probing molecular twist and tilt in aromatic self-assembled monolayers
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Using a nitrile tailgroup as a spectroscopic marker, both twist and tilt of the aromatic backbones in several typical aromatic SAMs on Au(111) have been directly determined in a single experiment. Whereas the exact value of the twist angle depends on the molecular architecture, it was found to be quite noticeable in all SAMs (40-50°) and close to the respective value for aromatic bulk systems (32°). Copyright
- Ballav, Nirmalya,Schuepbach, Bjoern,Dethloff, Ole,Feulner, Peter,Terfort, Andreas,Zharnikov, Michael
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p. 15416 - 15417
(2008/09/19)
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- Dicationic near-linear biphenyl benzimidazole derivatives as DNA-targeted antiprotozoal agents
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A series of near-linear biphenyl benzimidazole diamidines 5a-h were synthesized from their respective diamidoximes (4a-h), through the bis-O-acetoxyamidoxime, followed by hydrogenation in glacial acetic acid/ethanol in the presence of Pd-C. Compounds 4a-h
- Ismail, Mohamed A.,Batista-Parra, Adalgisa,Miao, Yi,Wilson, W. David,Wenzler, Tanja,Brun, Reto,Boykin, David W.
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p. 6718 - 6726
(2007/10/03)
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- DICATIONIC TRIARYL ANALOGS AS ANTI-PROTOZOAN AGENTS
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Novel dicationic, heterocyclic triaryl compounds are useful in the treatment of microbial infections, such as Trypanosoma brucei rhodesiense infection and Plasmodium falciparum infection. These compounds are accordingly useful in treating second-stage human African trypanosomiasis. Pharmaceutical formulations comprising these compounds can be used in methods of treating microbial infections.
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Page/Page column 75
(2008/06/13)
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- A convenient microwave assisted arylzinc generation-Negishi coupling protocol
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Arylzinc reagents were readily prepared from aryl iodides using a Zn-Cu couple in a microwave environment. A sequential arylzinc formation-Negishi cross-coupling protocol suitable for parallel high-throughput synthesis has been developed.
- Mutule, Ilga,Suna, Edgars
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p. 3909 - 3912
(2007/10/03)
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- PIPERIDINES USEFUL FOR THE TREATMENT OF CENTRAL NERVOUS SYSTEM DISORDERS
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The invention relates to compounds which are substituted chiral or achiral derivatives of 3- or 4- aminopiperidine of the general formula (I). The invention also concerns related aspects including processes for the preparation of the compounds, pharmaceutical compositions containing one or more compounds of general formula I and especially their use as inhibitors of β-secretases.
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- SUBSTITUTED 3- AND 4- AMINOMETHYLPIPERIDINES FOR USE AS BETA-SECRETASE IN THE TREATMENT OF ALZHEIMER’S DISEASE
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The invention relates to novel compounds, which are substituted chiral or achiral derivatives of 3- or 4- aminomethylpiperidine of the general formula (I). The invention also concerns related aspects including processes for the preparation of the compounds, pharmaceutical compositions containing one or more compounds of general formula (I) and especially their use as inhibitors of beta-secretases for the treatment of Alzheimer’s disease.
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Page/Page column 47
(2008/06/13)
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- Catalyst for aromatic C—O, C—N, and C—C bond formation
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The present invention is directed to a transition metal catalyst, comprising a Group 8 metal and a ligand having the structure wherein R, R′ and R″ are organic groups having 1-15 carbon atoms, n=1-5, and m=0-4. The present invention is also directed to a method of forming a compound having an aromatic or vinylic carbon-oxygen, carbon-nitrogen, or carbon-carbon bond using the above catalyst. The catalyst and the method of using the catalyst are advantageous in preparation of compounds under mild conditions of approximately room temperature and pressure.
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- Air stable, sterically hindered ferrocenyl dialkylphosphines for palladium-catalyzed C-C, C-N, and C-O bond-forming cross-couplings
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Pentaphenylferrocenyl di-tert-butylphosphine has been prepared in high yield from a two-step synthetic procedure, and the scope of various cross-coupling processes catalyzed by complexes bearing this ligand has been investigated. This ligand creates a remarkably general palladium catalyst for aryl halide amination and for Suzuki coupling. Turnovers of roughly 1000 were observed for aminations with unactivated aryl bromides or chlorides. In addition, complexes of this ligand catalyzed the formation of selected aryl ethers under mild conditions. The reactions encompassed electron-rich and electron-poor aryl bromides and chlorides. In the presence of catalysts containing this ligand, these aryl halides coupled with acyclic or cyclic secondary alkyl- and arylamines, with primary alkyl- and arylamines, and with aryl- and primary alkylboronic acids. These last couplings provide the first general procedure for reaction of terminal alkylboronic acids with aryl halides without toxic or expensive bases. The ligand not only generates highly active palladium catalysts, but it is air stable in solution and in the solid state. Palladium(0) complexes of this ligand are also air stable as a solid and react only slowly with oxygen in solution.
- Kataoka, Noriyasu,Shelby, Quinetta,Stambuli, James P.,Hartwig, John F.
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p. 5553 - 5566
(2007/10/03)
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- Liquid crystals
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Compounds of the formula STR1 wherein n stands for the number 0 or 1; the rings A1, A2 and A3 represent 1,4-phenylene, 2-fluoro-1,4-phenylene or trans-1,4-cyclohexylene or one of these rings also represents a 2,5-disubstituted pyrimidine ring or a trans-2,5-disubstituted m-dioxane ring; X1 represents a single covalent bond, --COO--, --OOC--, --CH2 CH2 --, p--C6 H4 --, --CH2 CH2 --p-- C6 H4 --, --CH2 CH2 --p--C6 H4 --CH2 CH2 -- or, insofar as the rings A1 and A2 represent 1,4-phenylene, also --NON--; R2 represents 1E-alkenyl, 2Z-alkenyl, 3E-alkenyl, 4-alkenyl or alkenyloxy, with the proviso that the oxygen atom in alkenyloxy is linked with a saturated carbon atom; and R1 signifies 1E-alkenyl, 2Z-alkenyl, 3E-alkenyl, 4-alkenyl or, insofar as R2 represents alkenyloxy, also alkyl, their manufacture, as well as liquid crystalline mixtures and the use for electro-optical purposes.
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- Novel liquid crystal mixtures
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Liquid crystalline mixtures containing compounds of the formula STR1 wherein n stands for the number 0 or 1; X1 and X2 denote single covalent bonds or one of the symbols X1 and X2 also denotes --COO--, --OOC-- or --CH2 CH2 --; the rings A1, A2 and A3 represent 1,4-phenylene, 2-fluoro-1,4-phenylene or trans-1,4-cyclohexylene or one of these rings also represents a 2,5-disubstituted pyrimidine ring or a trans-2,5-disubstituted m-dioxane ring; R1 signifies 4-alkenyl or on a cyclohexyl ring also 2Z-alkenyl; and R2 denotes alkyl, alkoxy, --CN or --NCS, as well as the manufacture of these compounds and the use for electro-optical purposes are described.
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