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41.
Asymmetric,Three‐Component,One‐Pot Synthesis of Spiropyrazolones and 2,5‐Chromenediones from Aldol Condensation/NHC‐Catalyzed Annulation Reactions
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Dr. Lei Wang Sun Li Dr. Pankaj Chauhan Dr. Daniel Hack Arne R. Philipps Dr. Rakesh Puttreddy Prof. Dr. Kari Rissanen Prof. Dr. Gerhard Raabe Prof. Dr. Dieter Enders 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(15):5123-5127
A novel one‐pot, three‐component diastereo‐ and enantioselective synthesis of spiropyrazolones has been developed involving the aldol condensation of an enal to generate α,β‐unsaturated pyrazolones, which react with a second equivalent of enal through an N‐heterocyclic carbene (NHC)‐catalyzed [3+2] annulation. The desired spirocyclopentane pyrazolones are obtained in moderate to good yields and good to excellent stereoselectivities. Alternatively, starting from cyclic 1,3‐diketones, 2,5‐chromenediones are available through [2+4] annulation. 相似文献
42.
[structure: see text] Sterically hindered tetraaminomethylated resorcarenes form inclusion complexes in CDCl(3) with acetonitrile and acetaldehyde, which are kinetically stable on the NMR time scale at 233 K. 相似文献
43.
We describe a new mechanism for reheating the Universe through evaporation of a surface charge of a fragmented inflaton condensate. We show that for a range of Yukawa coupling of the inflaton to the matter sector evaporation gives rise to a much smaller reheat temperature compared to the standard perturbative decay. As a consequence, reheating through a surface effect could solve the gravitino and moduli overproduction problem in inflationary models without fine tuning the Yukawa sector. 相似文献
44.
45.
Günter Haufe Thomas C. RosenOliver G.J. Meyer R. FröhlichKari Rissanen 《Journal of fluorine chemistry》2002,114(2):189-198
Monofluorinated cyclopropanecarboxylates are available in racemic or optically active form by transition metal-catalyzed reactions of vinylfluorides with diazoacetates. From α-fluorostyrene and tert-butyl diazoacetate in the presence of 2 mol% of an enantiopure bis(oxazoline) copper complex, a 81:19 mixture of tert-butyl trans- and cis-2-fluoro-2-phenylcyclopropanecarboxylates was obtained with high enantiomeric excess (ee) of 93 or 89%, respectively. The corresponding racemic ethylesters were used as starting materials for the synthesis of carboxamides, of the cis- and trans-isomers of analogues of tranylcypromine, an anti-depressive drug and several of its homologous fluorinated cyclopropylmethyl and cyclopropylethyl amines. Corresponding enantiopure cyclopropylmethanols and several of their derivatives were synthesized also. Solid state structures of a selection of these compounds were examined by X-ray crystallography. Particularly, the cis-configurated fluorinated phenylcyclopropane derivatives showed extremely close intermolecular CH?FC contacts. The shortest of such distances (2.17 Å) was found in the N-(4-bromophenyl)carbamate of (1S,2R)-(2-fluoro-2-phenylcyclopropyl)methanol. 相似文献
46.
Michael Müller Prof. Dr. Markus Albrecht Verena Gossen Tanja Peters Andreas Hoffmann Prof. Dr. Gerhard Raabe Dr. Arto Valkonen Prof. Kari Rissanen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(41):12446-12453
The directionality of interaction of electron‐deficient π systems with spherical anions (e.g,. halides) can be controlled by secondary effects like NH or CH hydrogen bonding. In this study a series of pentafluorophenyl‐substituted salts with polyhalide anions is investigated. The compounds are obtained by aerobic oxidation of the corresponding halide upon crystallization. Solid‐state structures reveal that in bromide 2 , directing NH–anion interactions position the bromide ion in an η1‐type fashion over but not in the center of the aromatic ring. The same directing forces are effective in corresponding tribromide salt 3 . In the crystal, the bromide ion is paneled by four electron‐deficient aromatic ring systems. In addition, compounds 4 and 6 , which have triiodide and the rare tetraiodide dianion as anions, are described. Computational studies reveal that the latter is highly unstable. In the present case it is stabilized by the crystal lattice, for example, by interaction with electron‐deficient π systems. 相似文献
47.
Cametti M Ilander L Valkonen A Nieger M Nissinen M Nauha E Rissanen K 《Inorganic chemistry》2010,49(24):11473-11484
Ditopic salophen-UO(2) receptors 1-4 and 7 co-crystallize with tetramethylammonium (TMA) chloride and fluoride salts producing good quality crystals amenable for X-ray diffraction characterization. The arrangement of the receptor and salt units in the crystal lattice is such that tetrameric ball-shaped assemblies are formed, where an inner cluster of four TMA cations are surrounded by an outer shell of four UO(2)-bound anions. These elaborate architectures, which occur in all cases, regardless of a certain degree of structural modification on the receptors, lead to lattices that belong to non-centrosymmetric (NCS) space groups. Interestingly, the tetragonal symmetry of the tetrameric ball-shaped assemblies is either retained (I4?) or lost (R3c and I4?3d) at the lattice level, without compromising the NCS nature of the crystal lattices. The principal X-ray investigation on TMAX (X = Cl/F) co-crystals, that is, 1-(TMA)Cl, 2-(TMA)Cl, 3-(TMA)Cl, 4-(TMA)Cl, 7-(TMA)Cl, and 7-(TMA)F, is accompanied by NMR and electrospray ionization (ESI) mass spectrometry studies to gather additional insight on the modality of formation of the solid state structures observed. The important role of cation-π interactions in the receptor-salt recognition process is renewed and strengthened by comparison with NMR titration data with a novel reference compound, the salophen-UO(2) complex 8. Given the importance of NCS and polar crystalline solids in the development of functional materials, this study shows that this property can be introduced into elaborate host-guest systems, as those which assemble in the architectures described here, thus expanding its field of applicability. 相似文献
48.
Tero Tuuttila Manu Lahtinen Juhani Huuskonen Kari Rissanen 《Thermochimica Acta》2010,497(1-2):109-116
The thermal properties of twelve Janus-type dendrimers up to the second generation were evaluated by termogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Compounds consist of the dendritic bisMPA based polyester moieties, and either 3,4-bis-dodecyloxybenzoic acid, 3,5-bis-dodecyloxybenzoic acid or 3,4,5-tris-dodecyloxybenzoic acid moieties, attached to opposite sides of the pentaerythritol core. The thermal stability of the compounds was evaluated by TGA, displaying onset decomposition temperatures (Td) at around 250 °C. DSC measurements upon heating and cooling confirmed that OH terminated Janus dendrimers featuring large polarity difference in opposite sides display liquid crystalline phases with exception of 3,5-type G1 dendrimer; while acetonide terminated dendrimers displayed merely melting transitions. Dendrimers having terminal alkyl chains at positions 3,4 or 3,4,5 in aromatic moieties exhibited enantiotropic mesophases. However, the thermal behavior of the dendrimers with 3,5-substitution pattern was different: the 3,5-type G1 dendrimer exhibit a lack of mesomorphic transition, and in the case of the 3,5-type G2 dendrimer, the mesophase was absent in the first heating scan but was observed during the subsequent cooling and heating scans at the rate of 10 °C/min. 相似文献
49.
Satoshi Migita Akito Tateishi Kari Keinänen Tetsuya Haruyama 《Analytical and bioanalytical chemistry》2010,396(3):1153-1157
Bioassay models of neural functions must lend themselves to high-throughput analysis in neural drug discovery. However, smart
analysis methods for these functions have not yet been fully established. Here, we describe the development of a synapse model
for cell-based biosensing. The engineered synapse model cell expresses ionotropic glutamate receptor on its surface, like
the neural postsynaptic membrane. The advantages of the model cell are the ease of handling and reproducibility as compared
with the cultured neural cell, and it can be employed to evaluate receptor function through ion flux analysis. The agonist-induced
sodium influx was monitored as an agonist concentration-dependent increase in the observed fluorescence signal. Furthermore,
we found that our model cell enables the correction of uneven cellular signal levels using a reporter system. Our engineered
synapse model cell can be employed as a powerful tool for the screening of lead substances in pharmaceutical high-throughput
analysis. 相似文献
50.
Totti Laitinen Sara Herrero Martín Jevgeni Parshintsev Tuulia Hyötyläinen Kari Hartonen Marja-Liisa Riekkola Markku Kulmala José Luis Pérez Pavón 《Journal of chromatography. A》2010,1217(1):151-159
Organic compounds in atmospheric nanoparticles have an effect on human health and the climate. The determination of these particles is challenged by the difficulty of sampling, the complexity of sample composition, and the trace-level concentrations of the compounds. Meeting the challenge requires the development of sophisticated sampling systems for size-resolved particles and the optimization of sensitive, accurate and simple analytical techniques and methods. A new sampling system is proposed where particles are charged with a bipolar charger and size-segregated with a differential mobility analyzer. This system was successfully used to sample particles from wood pyrolysis with particle sizes 30–100 nm. Particles were analyzed by four techniques: comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry, gas chromatography–time-of-flight mass spectrometry, gas chromatography–quadrupole mass spectrometry, and aerosol mass spectrometry (aerosol MS). In the chromatographic techniques, particles were collected on a filter and analyzed off-line after sample preparation, whereas in the aerosol MS, particle analysis was performed directly from the particle source. Target compounds of the samples were polyaromatic hydrocarbons and n-alkanes. The analytical techniques were compared and their advantages and disadvantages were evaluated. The sampling system operated well and target compounds were identified in low concentrations. 相似文献