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941.
Attempts to perform the OsO4-catalyzed enantioselective base-free aminohydroxylation of β,β-disubstituted enoates are described. Low yields and racemic products were obtained in the presence of standard chiral ligands, suggesting the occurrence of a “Second Cycle” process due to slow hydrolysis of the amino alcohol product from the Os metal center. Support for this hypothesis was provided by the slightly improved enantioselectivity (60:40 er) obtained with an amino alcohol ligand. Based on density functional theory calculations, it is proposed that the lack of significant enantioselectivity is due to a low-energy (3 + 2) oxo/imido cycloaddition transition state without the chiral ligand in the Second Cycle that outcompetes protonolysis in the First Cycle. 相似文献
942.
The development of improved syntheses of PPARγ-sparing,insulin sensitizing thiazolidinedione-ketones
Steven P. Tanis Jerry R. Colca Timothy T. Parker Gerald D. Artman Scott D. Larsen Robert C. Gadwood James R. Zeller 《Tetrahedron letters》2019,60(33):150931
Ketones 2 (MSDC-0160) and 3 (MSDC-0602) had been selected for clinical development, however their initial syntheses were considered suboptimal for application deep into clinical trials. Difficulties ranging from the nature of the starting material, alcohol oxidation problems, epoxide opening regioisomeric issues, and endgame ketone redox problems had been encountered. Direct ketone introduction/maintenance was desired for maximum efficiency and convergence was found to be critically dependent upon the acidity of the nucleophilic species (13, 18) and the use of pre- or post-alkylative oximino-ether/oxime protection (vide infra). Improvements in overall yield for the syntheses of 2 (MSDC-0160) and 3 (MSDC-0602) from 20% (2) and 31% (3) respectively, to 44% (2) and 59% (3) were realized. 相似文献
943.
944.
Prof. Peter A. Beckmann Prof. Paul R. Rablen Dr. Jason Schmink Dr. Steven T. Szewczyk Prof. Arnold L. Rheingold 《Chemphyschem》2019,20(21):2887-2894
We investigate the relationship between structure (crystal and molecular) and tert-butyl and methyl group dynamics in 2-(tert-butyl)-9-(4-(tert-butyl)phenyl)anthracene. Powder and single-crystal X-ray diffraction, taken together, show that different polycrystalline samples recrystallized from different solvents have different amounts of at least four polymorphs (crystallites having different crystal structures), of which we have identified three by single crystal X-ray diffraction. The molecules in the asymmetric units of the different crystal structures differ by the dihedral angle the tert-butylphenyl group makes with the anthracene moiety. Ab initio electronic structure calculations on the isolated molecule show that very little intramolecular energy is required to change this angle over a range of about 60° which is probably the origin of the concomitant polymorphism (crystals of more than one polymorph in a polycrystalline sample). Solid state 1H nuclear magnetic resonance (NMR) spin-lattice relaxation experiments support the powder and single-crystal X-ray results and provide average NMR activation energies (closely related to rotational barriers) for the rotation of the tert-butyl groups and their constituent methyl groups. These barriers have both an intramolecular and an intermolecular component. The latter is sensitive to the crystal structure. The intramolecular components of the rotational barriers of the two tert-butyl groups in the isolated molecule are investigated with ab initio electronic structure calculations. 相似文献
945.
Shub DE Durlach NI Colburn HS 《The Journal of the Acoustical Society of America》2008,123(6):4421-4433
The ability to make judgments about the stimulus at one ear when a stimulus is simultaneously presented to the other ear was tested. Specifically, subjects discriminated the level of a 600 Hz target tone presented at the left ear while an identical-frequency distractor was simultaneously presented at the other ear. When there was no distractor, threshold was 0.7 dB. Threshold increased to 1.1 dB when a distractor with a fixed phase and level was introduced contra-aurally to the target. Further increases in threshold were observed when an across-presentation variability was introduced into the distractor phase (threshold of 1.6 dB) or level (threshold of 5.8 dB). When both the distractor level and phase varied, the largest threshold of 7.3 dB was obtained. These increases in threshold cannot be predicted by common binaural models, which assume that a target stimulus at one ear can be processed without interference from the stimulus at the nontarget ear. The measured thresholds are consistent with a model that utilizes two binaural dimensions that roughly correspond to the loudness and the position of a fused binaural image. The results show that, with binaurally fused tonal stimuli, subjects are unable to listen to one ear. 相似文献
946.
Alexander Bass Seth Putterman Barry Merriman Steven J. Ruuth 《Journal of computational physics》2008,227(3):2118-2129
We propose a symmetry reduction technique whereby molecular dynamics (MD) simulations for spherically symmetric gas bubbles can be accelerated. Results for an imploding Xenon bubble containing 50 million particles—the smallest measured sonoluminescing system—are presented. 相似文献
947.
Complex random states have the statistical properties of the Gaussian and circular unitary ensemble eigenstates of random matrix theory. Even though their components are correlated by the normalization constraint, it is nevertheless possible to derive compact analytic formulas for their extreme values' statistical properties for all dimensionalities. The maximum intensity result slowly approaches the Gumbel distribution even though the variables are bounded, whereas the minimum intensity result rapidly approaches the Weibull distribution. Since random matrix theory is conjectured to be applicable to chaotic quantum systems, we calculate the extreme eigenfunction statistics for the standard map with parameters at which its classical map is fully chaotic. The statistical behaviors are consistent with the finite-N formulas. 相似文献
948.
Magnetic edge-state excitons in zigzag graphene nanoribbons 总被引:1,自引:0,他引:1
We present first-principles calculations of the optical properties of zigzag-edged graphene nanoribbons (ZGNRs) employing the GW-Bethe-Salpeter equation approach with the spin interaction included. Optical response of the ZGNRs is found to be dominated by magnetic edge-state-derived excitons with large binding energy. The absorption spectrum is composed of a characteristic series of exciton states, providing a possible signature for identifying the ZGNRs. The edge-state excitons are charge-transfer excitations with the excited electron and hole located on opposite edges; they moreover induce a spin transfer across the ribbon, resulting in a photoreduction of the magnetic ordering. These novel characteristics are potentially useful in the applications. 相似文献
949.
We evaluate the Poynting vector generated by a heavy quark moving through a thermal state of N=4 gauge theory using the gauge-string duality. A significant diffusion wake is observed as well as a Mach cone. We discuss the ratio of the energy going into sound modes to the energy coming in from the wake. 相似文献
950.
Simultaneous detection of ultraviolet and infrared radiation in a single GaN/GaAlN heterojunction 总被引:1,自引:0,他引:1
Jayasinghe RC Ariyawansa G Dietz N Perera AG Matsik SG Yu HB Ferguson IT Bezinger A Laframboise SR Buchanan M Liu HC 《Optics letters》2008,33(21):2422-2424
Results are presented for a dual-band detector that simultaneously detects UV radiation in the 250-360 nm and IR radiation in the 5-14 microm regions with near zero spectral cross talk. In this detector having separate UV- and IR-active regions with three contacts (one common contact for both regions) allows the separation of the UV and IR generated photocurrent components, identifying the relative strength of each component. This will be an important development in UV-IR dual-band applications such as fire-flame detection, solar astronomy, and military sensing, eliminating the difficulties of employing several individual detectors with separate electronics-cooling mechanisms. 相似文献