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191.
Bean A Gronberg J Kutschke R Menary S Morrison RJ Nelson H Richman J Tajima H Schmidt D Sperka D Witherell M Procario M Yang S Daoudi M Ford WT Johnson DR Lingel K Lohner M Rankin P Smith JG Alexander JP Bebek C Berkelman K Besson D Browder TE Cassel DG Coffman DM Drell PS Ehrlich R Galik RS Garcia-Sciveres M Geiser B Gittelman B Gray SW Hartill DL Heltsley BK Honscheid K Jones C Kandaswamy J Katayama N Kim PC Kreinick DL Ludwig GS Masui J Mevissen J Mistry NB Ng CR Nordberg E O'Grady C 《Physical review letters》1993,70(2):138-142
192.
193.
Structurally novel cyclitols, 1-aryl-1-deoxyconduritols F, were efficiently prepared from d-xylose, utilizing RCM as a key step. Various aromatic residues were incorporated in the cyclitol skeleton with total stereochemical control, utilizing a diastereoselective aryl cuprate addition to a gamma-alkoxy enoate. The synthetic route establishes a firm foundation for a practical synthesis of the antitumor alkaloid pancratistatin and its aryl analogues. [structure: see text] 相似文献
194.
Organically templated thorium compounds were synthesized for the first time under hydrothermal conditions; the piperazine containing compound consists of 2-D layers, while the 2-methylpiperazine phase contains unprecedented 1-D chains of face-sharing ThF9 polyhedra. 相似文献
195.
Alexander AJ 《The Journal of chemical physics》2005,123(19):194312
Equations to enable determination of the helicity (angular momentum orientation) of photofragments resulting from single-photon dissociation of an isotropic sample of molecules are presented. The symmetry of the photofragment distribution is illustrated by three-dimensional vector plots of the expectation values of projections of the fragment total angular momentum. Equations describing circular polarization of light in the spherical tensor basis are presented. Methods for the optical measurement of angular momentum orientation are discussed, including determination of the helicity of circularly polarized light by a quarter-wave plate or single Fresnel rhomb. 相似文献
196.
The oxidation of thiophene (1) with peracids in a strongly acidic environment yielded thiophen-2-one (4) as the product of an apparent direct hydroxylation of the thiophene aromatic ring together with the anticipated thiophene-S-oxide dimers, 2a,b, as the main products. Formation of the latter dimers can be rationalized in a straightforward manner by initial oxidation at the sulfur atom of thiophene (1) to yield thiophene-S-oxide followed by subsequent dimerization in a Diels-Alder type reaction. Trapping experiments in the presence of a competing dienophile indicated that thiophen-2-one (4) did not originate from the monomeric thiophene-S-oxide but was the product of an independent reaction pathway. The extent of thiophen-2-one (4) formation correlated with the acidity of the reaction medium and was suppressed in the presence of water, the latter presumably acting as a competing base. As evidenced by the use of 2,5-dideuterated thiophene (1-D), its mechanism of formation involved a 1,2-hydride shift, a feature commonly described in the peracid-mediated epoxidation of aromatic hydrocarbons and indicative for the occurrence of cationic intermediates. In agreement with all these observations we propose a mechanism involving initial protonation of thiophene followed by nucleophilic attack of the peracid in position 2 of the thiophene ring. Intramolecular epoxidation may lead to the formation of thiophene 2,3-epoxide as a highly reactive intermediate that then undergoes heterolytic ring opening and a 1,2-hydride shift to yield thiophen-2-one (4) after a final, acid-catalyzed, isomerization of the double bond. 相似文献
197.
Hünig I Painter AJ Jockusch RA Carçabal P Marzluff EM Snoek LC Gamblin DP Davis BG Simons JP 《Physical chemistry chemical physics : PCCP》2005,7(12):2474-2480
The gas phase structures of phenyl alpha- and beta-d-xylopyranoside (alpha- and beta-pXyl) and their mono-hydrates have been investigated using a combination of resonant two-photon ionization (R2PI), ultra-violet hole-burning and resonant infrared ion dip spectroscopy, coupled with density functional theory (DFT) and ab initio computation. The hole-burning experiments indicate the population of a single conformer only, in each of the two anomers. Their experimental and calculated infrared spectra are both consistent with a conformational assignment corresponding to the computed global minimum configuration. All three OH groups are oriented towards the oxygen atom (O1) on the anomeric carbon atom to form an all trans(ttt) counter-clockwise chain of hydrogen bonds. The mono-hydrates, alpha- and beta-pXyl(H(2)O) each populate two distinct structures in the molecular beam environment, with the water molecule inserted between OH4 and OH3 or between OH3 and OH2 in alpha-pXyl(H2O), and between OH2 and O1 in either of two alternative orientations, in beta-pXyl(H2O). In all of the mono-hydrated xyloside complexes, the water molecule inserts into the weakest link of the sugar molecules' hydrogen-bonded chain of hydroxy groups, creating a single extended chain, strengthened by co-operativity. The all-trans configuration of the xylose moiety is retained and the mono-hydrate structures correspond to those calculated to lie at the lowest relative energies. 相似文献
198.
We have demonstrated that a bipyrimidinylplatinum-polyoxometalate, [Pt(Mebipym)Cl2]+[H4PV2Mo10O40]-, supported on silica is an active catalyst for the aerobic oxidation of methane to methanol in water under mild reaction conditions. Further oxidation of methanol yields acetaldehyde. The presence of the polyoxometalate is presumed to allow the facile oxidation of a Pt(II) intermediate to a Pt(IV) intermediate and to aid in the addition of methane to the Pt catalytic center. 相似文献
199.
Bauer RE Enkelmann V Wiesler UM Berresheim AJ Müllen K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(17):3858-3864
A series of first-generation polyphenylene dendrimers based on three different cores were prepared by Diels-Alder cycloaddition and their single-crystal structures were determined. Consisting exclusively of interlocked, twisted phenyl rings, these polyphenylene nanostructures have exciting structural and dynamic properties. Single crystals of dendrimers, suitable for X-ray structure analysis, were grown from different solvent mixtures by slow evaporation at room temperature. It should be pointed out that one of the described polyphenylene dendrimers represents up to now the biggest oligophenylene nanostructure from which crystallographic data is available. 相似文献
200.
Allenic acids are found to add to dicyclohexylcarbodiimide affording, in the presence of Et2NH, the 4H-1,3-oxazin-4-ones 5 via 4 . Under neutral conditions, they add to diaryl- or pyridyl(cyclohexyl)carbodiimides and triphenylketene imine to give the corresponding tricyclo[5.2.2.01,5]undeca-4,8,10-trien-3-ones 7 , 8 , 9 , and 12 . The allenic phenyl ester 13a dimerises, on heating in a [2+2] head-to-head fashion, to 14 but fails to undergo intramolecular Diels-Alder cyclization, to 15 . 相似文献