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71.
6-Trifluoromethyl-12-acylindolo[1,2-c]quinazolines are prepared in high yield through the palladium-catalyzed reaction of bis(o-trifluoroacetamidophenyl)acetylene with aryl or vinyl halides and triflates. The reaction, which tolerates a variety of important functional groups, probably involves the formation of a 3-acyl-2-(o-trifluoroacetamidophenyl)indole intermediate, followed by its cyclization to the indoloquinazoline product. [reaction: see text] 相似文献
72.
Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111) 总被引:2,自引:0,他引:2
Barth JV Weckesser J Trimarchi G Vladimirova M De Vita A Cai C Brune H Günter P Kern K 《Journal of the American Chemical Society》2002,124(27):7991-8000
We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems. 相似文献
73.
(R)-Phenylglycinol is shown to be an efficient building block for the synthesis of chiral amino diols in pure diastereomeric form by epoxide ring-opening reactions. The reaction with rac-trans-stilbene oxide gives [HOCH(2)-(R)-PhCH]NH[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-HNO(2)H(2)] in 32% yield, which can be methylated at nitrogen to give enantiomerically pure [HOCH(2)-(R)-PhCH]NCH(3)[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-MeNO(2)H(2)]. These amino diol ligands have been used to prepare chiral dioxomolybdenyl complexes of the formula N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) (1) and N(R)-2(R)-3(R)-4(S)-(MeNO(2))MoO(2) (2). The absolute configuration at each stereocenter in the Mo(VI) complexes has been established by (1)H NOESY spectroscopy. The configuration determined for 1 has been confirmed by an X-ray analysis. Crystal data: orthorhombic P2(1)2(1)2(1), a =7.620(3), b = 13.589(2), c = 20.339(3) ?, Z = 4, R = 0.0336. The structure consists of a polymeric chain of N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) molecules connected through unsymmetrical Mo=O --> Mo bridges. Each metal center is coordinated in a distorted octahedral geometry by a cis dioxo unit and by two trans alkoxo atoms. The coordination polyhedron is completed by a nitrogen atom and by a bridging oxo oxygen atom from an adjacent molecule. Compound 2 catalyzes the oxidation of PPh(3) to OPPh(3) by DMSO through a mechanism that involves the intermediacy of a Mo(IV) species. 相似文献
74.
A novel 4-[4-(pentafluoro-λ⁶-sulfanyl)phenyl]-1,2,4-triazole-3,5-dione (5a) was synthesised as a potential [18F]radio-prosthetic group for radiolabelling peptides and proteins via selective bioconjugation with the phenolic side chains of tyrosine residues. Preliminary conjugation tests revealed the rapid hydrolysis of 5a under semi-aqueous conditions; these results led to further investigation into the electronic substituent effects of PTAD derivatives and corresponding hydrolytic stabilities. Five derivatives of 5a with para substituents of varying electron donating and withdrawing effects were synthesised for the investigation. The bioconjugation of these derivatives with model tyrosine was monitored in both aqueous and organic media in the presence of a variety of catalysts. From these investigations, we have found HFIP to be an effective catalyst when used in tandem with DCM as a solvent to give PTAD-tyrosine conjugate products (6a–f) in satisfactory to good yields (54–79%), whereas analogous reactions performed in acetonitrile were unsuccessful. The discovery of this system has allowed for the successful conjugation of electron-deficient PTAD derivatives to tyrosine, which would otherwise be unachievable under aqueous reaction conditions. The inclusion of these electron-deficient, fluorinated PTAD derivatives for use in the PTAD-tyrosine conjugation will hopefully broaden their applicability within fields such as 19F-MRI and PET imaging. 相似文献
75.
Raffaele Sacchi Giandomenico Corrado Boris Basile Daniele Mandarello Maria Luisa Ambrosino Antonello Paduano Maria Savarese Nicola Caporaso Maria Aponte Alessandro Genovese 《Molecules (Basel, Switzerland)》2022,27(22)
‘Oliva di Gaeta’ is almost certainly the most important and well-known PDO denomination for table olives in Italy. Their production is based on a specific two-stage trade preparation called the ‘Itrana’ method. In this work, we investigated how variations in the duration of the initial water fermentation (i.e., 15 and 30 days) and the salt concentration (i.e., 6% and 8% NaCl) influence the chemical features, microbial dynamics, polyphenols, volatile organic compounds, and sensory features of ‘Oliva di Gaeta’. The time of the addition of salt did not affect the final concentration in the brine, but a longer initial water fermentation (before salt addition) led to lower pH values. The bacterial count constantly increased until the salt addition (i.e., either 15 or 30 days), while the yeast population peaked on day 30. Generally, the two different salt concentrations did not affect the count of microorganisms at the end of fermentation, with the only exception being a higher lactic acid bacteria count for the treatment with 6% salt added at 30 days. At commercial maturity, the crucial bitter tastant oleuropein was not completely removed from the drupes, and differences in salt concentration and the length of the first-stage water fermentation did not influence its content at the end of olive curing. Richer volatile profiles of olives were detected with higher-salt treatments, while the combination of low salt and early saline treatment provided a more distinct profile. Longer initial water fermentation caused a small increase in some phenolic compounds (e.g., iso-verbascoside, verbascoside, and hydroxytyrosol-glucoside). A panel test indicated that salt application at 30 days resulted in a more “Sour” and “Bitter” taste, irrespective of the salt concentration. The low salt concentration coupled with the late saline treatment resulted in more “Fruity” notes, probably due to the higher production of esters by lactobacilli. The slightly bitter perception of the olives was consistent with the partial removal of oleuropein. Our work revealed the characteristics of the ‘Itrana’ method and that the variation in salt concentration and its time of application changes parameters ranging from the microbial dynamics to the sensory profile. Specifically, our data indicate that 6% NaCl coupled with a longer initial water fermentation is the most different condition: it is less effective in blocking microbial growth but, at the same time, is more potent in altering the nutritional (e.g., polyphenols) and sensorial qualities (e.g., bitterness and fruitiness) of ‘Oliva di Gaeta’. 相似文献
76.
Martina Bottoni Giovanna Baron Francesca Gado Fabrizia Milani Laura Santagostini Lorenzo Colombo Paola Sira Colombo Elisabetta Caporali Alberto Spada Marco Biagi Claudia Giuliani Piero Bruschi Giancarlo Aldini Gelsomina Fico 《Molecules (Basel, Switzerland)》2022,27(23)
A multidisciplinary investigation on Achillea moschata Wulfen (Asteraceae) is outlined herein. This work, part of the European Interreg Italy–Switzerland B-ICE project, originated from an ethnobotanical survey performed in Chiesa in Valmalenco (Sondrio, Lombardy, Northern Italy) in 2019–2021 which highlighted this species’ relevance of use in folk medicine to treat gastrointestinal diseases. In addition, this contribution included analyses of the: (a) phytochemical profile of the aqueous and methanolic extracts of the dried flower heads using LC-MS/MS; (b) morpho-anatomy and histochemistry of the vegetative and reproductive organs through Light, Fluorescence, and Scanning Electron Microscopy; (c) biological activity of the aqueous extract concerning the antioxidant and anti-inflammatory potential through cell-based in vitro models. A total of 31 compounds (5 phenolic acids, 13 flavonols, and 13 flavones) were detected, 28 of which included in both extracts. Covering and secreting trichomes were observed: the biseriate 10-celled glandular trichomes prevailing on the inflorescences represented the main sites of synthesis of the polyphenols and flavonoids detected in the extracts, along with volatile terpenoids. Finally, significant antioxidant and anti-inflammatory activities of the aqueous extract were documented, even at very low concentrations; for the first time, the in vitro tests allowed us to formulate hypotheses about the mechanism of action. This work brings an element of novelty due to the faithful reproduction of the traditional aqueous preparation and the combination of phytochemical and micromorphological research approaches. 相似文献
77.
Tinuccia Dettori Giuseppina Sanna Andrea Cocco Gabriele Serreli Monica Deiana Vanessa Palmas Valentina Onnis Luca Pilia Nicola Melis Davide Moi Paola Caria Francesco Secci 《Molecules (Basel, Switzerland)》2022,27(24)
A series of 6- and 6,8-halocoumarin derivatives have been investigated as potential antiproliferative compounds against a panel of tumor and normal cell lines. Cytotoxic effects were determined by the MTT method. To investigate the potential molecular mechanism involved in the cytotoxic effect, apoptosis assay, cell cycle analysis, reactive oxygen species (ROS), and reduced glutathione analysis were performed. Among the screened compounds, coumarins 6,8-dibromo-2-oxo-2H-chromene-3-carbonitrile 2h and 6,8-diiodo-2-oxo-2H-chromene-3-carbonitrile 2k exhibited the most antiproliferative effect in thyroid cancer-derived cells TPC-1. The apoptosis assay showed that both 2h and 2k induced apoptosis in TPC-1 thyroid cancer cells. According to these experiments, both coumarins induced a slight increase in TPC-1 cells in the G2/M phase and a decrease in the S phase. A significant increase in ROS levels was observed in TPC-1 treated with diiodocoumarin 2k, while the dibromocoumarin 2h induced a decrease in ROS in a dose and time-dependent manner. 相似文献
78.
Nicola Gigli 《Geometric And Functional Analysis》2012,22(4):990-999
We prove existence of optimal maps in non branching spaces with Ricci curvature bounded from below. The approach we adopt makes no use of Kantorovich potentials. 相似文献
79.
80.