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131.
The pyran-containing fragments 1 and 2 of AM3 have been synthesized from the common pyran intermediate 3. Careful orchestration of the alcohol protecting groups was necessary to facilitate deprotection of alcohol functionality in the presence of the chemically sensitive polyene chain. 相似文献
132.
Lynne H. Thomas Jacqueline M. Cole Chick C. Wilson 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(5):o296-o302
The crystal structure of 4‐chloronitrobenzene, C6H4ClNO2, a material that exhibits disorder in the solid state, is re‐examined using multiple‐temperature single‐crystal X‐ray diffraction. Our results show a marked improvement on previous crystal structure determinations and our comprehensive multiple temperature measurements help to rationalize the structural anomalies. 4‐Chloronitrobenzene exhibits twofold orientational disorder of the NO2/Cl substituents, with the molecule lying across an inversion centre. There is also evidence of large thermal motion, which exists at all temperatures and reflects the presence of significant disorder in this material. The nitro group shows possible libration, with one O atom exhibiting larger thermal motion than the other across the whole temperature range. This is explained by a difference in hydrogen‐bonding environment. 相似文献
133.
Hannedouche J Aillaud I Collin J Schulz E Trifonov A 《Chemical communications (Cambridge, England)》2008,(30):3552-3554
A facile method for the preparation of highly active and enantioselective yttrium precatalysts for asymmetric hydroamination of gem-disubstituted aminoalkenes, from the combination of YCl(3) or YCl(3)(THF)(3.5) with ligand (R)- and n-BuLi is described. 相似文献
134.
Variability of UV irradiance in Europe 总被引:1,自引:1,他引:0
Seckmeyer G Pissulla D Glandorf M Henriques D Johnsen B Webb A Siani AM Bais A Kjeldstad B Brogniez C Lenoble J Gardiner B Kirsch P Koskela T Kaurola J Uhlmann B Slaper H den Outer P Janouch M Werle P Gröbner J Mayer B de la Casiniere A Simic S Carvalho F 《Photochemistry and photobiology》2008,84(1):172-179
135.
Jean-Christophe Monbaliu Bernard Tinant Jacqueline Marchand-Brynaert 《Journal of Molecular Structure》2008,879(1-3):113-118
Reaction of N-(dienyl)-4-(R)-phenyloxazolidin-2-thione (1) with 1-diethoxyphosphoryl-1-buten-3-one (2a), methyl 3-(diethoxyphosphoryl)acrylate (2b) and 3-(diethoxyphosphoryl)acrylonitrile (2c) furnished the [4 + 2] cycloadducts 3a, 3b and 3c, respectively, as single stereoisomers, confirming the efficiency of the oxazolidin-2-thione chiral auxiliary in the facial discrimination of Diels–Alder reactions. The absolute configuration of the 3,4,5-trisubstituted cyclohexene derivatives (3a–c) was established by X-ray diffraction analysis. NMR studies confirmed the relative stereochemistries and showed two possible conformers in solution. 相似文献
136.
Delest B Nshimyumukiza P Fasbender O Tinant B Marchand-Brynaert J Darro F Robiette R 《The Journal of organic chemistry》2008,73(17):6816-6823
A divergent and regioselective synthesis of 1,2,4- and 1,2,5-trisubstituted imidazoles from a readily available (two steps) common intermediate has been developed. This methodology is based on the regiocontrolled N-alkylation of 1-(N,N-dimethylsulfamoyl)-5-iodo-2-phenylthio-1H-imidazole (10). When this intermediate is engaged in reaction with methyl triflate, selective formation of the corresponding 1,2,5-trisubsituted 1H-imidazole is observed. NMR studies have revealed that this regioselectivity can be accounted for by in situ rapid isomerization of 10 into its 1,2,4-isomer (13) followed by regiospecific N-alkylation of the latter. Conversely, when key intermediate 10 is slowly added to Meerwein's salt, isomerization can be constrained and regiospecific N-alkylation of 10 leads to 1,2,4-trisubstituted 1H-imidazole with a high selectivity. The general character of this methodology has been illustrated by showing that iodine in position 4 or 5 could be easily substituted by an aryl group by Suzuki coupling, whereas the phenylthio group at position 2 could, after oxidation into sulfone, be displaced by nucleophilic substitution. 相似文献
137.
Schelter EJ Veauthier JM Graves CR John KD Scott BL Thompson JD Pool-Davis-Tournear JA Morris DE Kiplinger JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(26):7782-7790
Reaction of two equivalents of [(C(5)Me(4)Et)(2)U(CH(3))(Cl)] (6) or [(C(5)Me(5))(2)Th(CH(3))(Br)] (7) with 1,4-dicyanobenzene leads to the formation of the novel 1,4-phenylenediketimide-bridged bimetallic organoactinide complexes [{(C(5)Me(4)Et)(2)(Cl)U}(2)(mu-{N==C(CH(3))-C(6)H(4)-(CH(3))C==N})] (8) and [{(C(5)Me(5))(2)(Br)Th}(2)(mu-{N==C(CH(3))-C(6)H(4)- (CH(3))C==N})] (9), respectively. These complexes were structurally characterized by single-crystal X-ray diffraction and NMR spectroscopy. Metal-metal interactions in these isovalent bimetallic systems were assessed by means of cyclic voltammetry, UV-visible/NIR absorption spectroscopy, and variable-temperature magnetic susceptibility. Although evidence for magnetic coupling between metal centers in the bimetallic U(IV)/U(IV) (5f(2)-5f(2)) complex is ambiguous, the complex displays appreciable electronic communication between the metal centers through the pi system of the dianionic diketimide bridging ligand, as judged by voltammetry. The transition intensities of the f-f bands for the bimetallic U(IV)/U(IV) system decrease substantially compared to the related monometallic ketimide chloride complex, [(C(5)Me(5))(2)U(Cl){-N==C(CH(3))-(3,4,5-F(3)-C(6)H(2))}] (11). Also reported herein are new synthetic routes to the actinide starting materials [(C(5)Me(4)Et)(2)U(CH(3))(Cl)] (6) and [(C(5)Me(5))(2)Th(CH(3))(Br)] (7) in addition to the syntheses and structures of the monometallic uranium complexes [(C(5)Me(4)Et)(2)UCl(2)] (3), [(C(5)Me(4)Et)(2)U(CH(3))(2)] (4), [(C(5)Me(4)Et)(2)U{-N==C(CH(3))-C(6)H(4)-C==N}(2)] (10), and 11. 相似文献
138.
The site-specific recognition of abasic sites and single base bulges in duplex DNA by sterically expansive rhodium metalloinsertors has been investigated. Through DNA photocleavage experiments, Rh(bpy)2(chrysi)3+ is shown to bind both abasic sites and single base bulges site-specifically and, upon irradiation, to cleave the backbone of the defect-containing DNA. Photocleavage titrations reveal that the metal complex binds DNA containing an abasic site with high affinity (2.6(5) x 106 M-1), comparably to the metalloinsertor and a CC mismatch. The complex binds single base bulge sites with lower affinity (approximately 105 M-1). Analysis of cleavage products and the correlation of affinities with helix destabilization suggest that Rh(bpy)2(chrysi)3+ binds both lesions via metalloinsertion, as observed for Rh binding at mismatched sites, a binding mode in which the mismatched or unpaired bases are extruded from the helix and replaced in the base stack by the sterically expansive ligand of the metalloinsertor. 相似文献
139.
Gadolinium chelate coated gold nanoparticles as contrast agents for both X-ray computed tomography and magnetic resonance imaging 总被引:1,自引:0,他引:1
Alric C Taleb J Le Duc G Mandon C Billotey C Le Meur-Herland A Brochard T Vocanson F Janier M Perriat P Roux S Tillement O 《Journal of the American Chemical Society》2008,130(18):5908-5915
Functionalized gold nanoparticles were applied as contrast agents for both in vivo X-ray and magnetic resonance imaging. These particles were obtained by encapsulating gold cores within a multilayered organic shell which is composed of gadolinium chelates bound to each other through disulfide bonds. The contrast enhancement in MRI stems from the presence of gadolinium ions which are entrapped in the organic shell, whereas the gold core provides a strong X-ray absorption. This study revealed that these particles suited for dual modality imaging freely circulate in the blood vessels without undesirable accumulation in the lungs, spleen, and liver. 相似文献
140.