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21.
Mingming Huang Dr. Jiefeng Hu Shasha Shi Dr. Alexandra Friedrich Johannes Krebs Prof. Dr. Stephen A. Westcott Prof. Dr. Udo Radius Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(24):e202200480
Defunctionalization of readily available feedstocks to provide alkenes for the synthesis of multifunctional molecules represents an extremely useful process in organic synthesis. Herein, we describe a transition metal-free, simple and efficient strategy to access alkyl 1,2-bis(boronate esters) via regio- and diastereoselective diboration of secondary and tertiary alkyl halides (Br, Cl, I), tosylates, and alcohols. Control experiments demonstrated that the key to this high reactivity and selectivity is the addition of a combination of potassium iodide and N,N-dimethylacetamide (DMA). The practicality and industrial potential of this transformation are demonstrated by its operational simplicity, wide functional group tolerance, and the late-stage modification of complex molecules. From a drug discovery perspective, this synthetic method offers control of the position of diversification and diastereoselectivity in complex ring scaffolds, which would be especially useful in a lead optimization program. 相似文献
22.
Thomas Wiesner Dr. Zhu Wu Dr. Jie Han Prof. Dr. Lei Ji Dr. Alexandra Friedrich Dr. Ivo Krummenacher Michael Moos Prof. Dr. Christoph Lambert Prof. Dr. Holger Braunschweig Benjamin Rudin Dr. Hilmar Reiss Olena Tverskoy Dr. Frank Rominger Prof. Dr. Andreas Dreuw Prof. Dr. Todd B. Marder Dr. Jan Freudenberg Prof. Dr. Uwe H. F. Bunz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(69):e202201919
Tetraiodotetraazapentacene I4TAP , the last missing derivative in the series of halogenated silylated tetraazapentacenes, was synthesized via condensation chemistry from a TIPS-ethynylated diaminobenzothiadiazol in three steps. Single and double reduction furnished its air-stable monoanion and relatively air-stable dianion, both of which were characterized by crystallography. All three species are structurally and spectroscopically compared to non-halogenated TAP and Br4TAP . I4TAP is an n-channel material in thin-film transistors with average electron mobilities exceeding 1 cm2 (Vs)−1. 相似文献
23.
Sebastian Pfadler Micha Löffler Friedrich Dinkelacker Alfred Leipertz 《Experiments in fluids》2005,39(2):375-384
The turbulence and temperature field of Bunsen-type turbulent lean methane/air flames has been investigated using planar laser Rayleigh scattering (PLRS) and stereo particle image velocimetry (stereo PIV). Temporally averaged reaction progress variable plots have been computed from PLRS measurements in order to provide a basis with regards to the verification of computational fluid dynamics (CFD) models. Turbulence was characterised by stereo PIV in one plane for all three velocity components. Averaged velocity fields have been calculated, as well as Reynolds-decomposed fluctuation vector fields. Conditioned root mean square (RMS) values of the turbulent fluctuations in terms of unburnt and burnt gas could be determined by making use of the information gained from a threshold setting procedure in the PIV raw images. Furthermore, several length scales were measured indirectly from PIV vector plots. In this context, all integral length scales being accessible with stereo PIV were computed separately for the burnt and unburnt regions and were compared to each other. It could be observed that all integral length scales increased in the burnt zone. Additionally, the conditioned Taylor and Kolmogorov lengths have been extracted from the PIV field data, derived either from the zero-radius curvature of the correlation function or from common turbulence theory relations. 相似文献
24.
Direct Numerical Simulation (DNS) and linear analysis of a shock interacting with incompressible and compressible isotropic turbulence is conducted. A dependence of amplification ratios on the degree of compressibility of the incoming flow is found. It can be shown that the enhancement of rms values of turbulent quantities across the shock varies according to the ratio of compressible to incompressible kinetic energy (exact definition see eq. 8). Inflow conditions with high values of display reduced amplification ratios of TKE and thermodynamic quantities while vorticity fluctuations are enhanced more strongly. The different behaviour of the turbulent kinetic energy (TKE) is due to the reduced pressure diffusion term in the TKE-equation. Experiments show qualitatively a similar behaviour as the simulation with incompressible inflow conditions, but they could so far not confirm our findings of reduced amplification rates in the compressible case, one of the reasons being the lack of knowledge of all flow parameters upstream of the shock front and the inability to generate isotropic turbulence in real life experiments. For the DNS we use a third order in space shock-capturing scheme based on the ENO algorithm of Harten [10] together with an approximate Riemann solver. This non-TVD scheme turned out to have many advantages over other common Godunov-type high resolution schemes for the specific problem of a shock interacting with turbulent fields. 相似文献
25.
Local fracture resistance (FR) of short (SGF) and discontinuous long glass fibre (LGF) reinforced polypropylene (PP) was predicted using the ‘microstructural efficiency concept’ together with a simulation program for fibre orientation in injection molding. The ‘microstructural efficiency concept’ describes the relation between microstructural parameters such as the fibre content, the fibre aspect ratio and the processing (injection molding) induced layer structure taking also into account the local fibre orientation. The local fibre orientation in injection molding was predicted with the MOLDFLOW®-software. The predicted local FR was compared with the measured one, which was determined by using compact tension samples and linear elastic fracture mechanics (LEFM). The comparison showed, that for SGF-PP good consistence between the predicted and measured FR existed, for LGF-PP the discrepancy was higher. Yet for both materials, the ‘microstructural efficiency concept’ together with the results obtained from the simulation of the fibre orientation can be used for FR prediction of an injection molded workpiece. 相似文献
26.
In linear elasticity, we decompose the elasticity tensor into two irreducible pieces with 15 and 6 independent components, respectively. The vanishing of the piece with 6 independent components corresponds to the Cauchy relations. Thus, for the first time, we recognize the group-theoretical underpinning of the Cauchy relations. 相似文献
27.
The evolution of incompressible and compressible isotropic 2-d turbulent fields interacting with a normal shock wave up to Mach numbers of 2.4 was investigated by means of direct numerical simulation using an ENO scheme. A comparison of statistics with linear analysis results is presented. Vorticity amplification in the DNS agrees well with the linear theory. Energy spectra are enhanced more in the small scales than in the large scales for incoming incompressible turbulence. The amplification rate for initially compressible turbulence is comparatively small. 相似文献
28.
Christophe?BrunEmail author Rainer?Friedrich Carlos?B.?da Silva 《Theoretical and Computational Fluid Dynamics》2006,20(1):1-21
A new subgrid scale (SGS) modelling concept for large-eddy simulation (LES) of incompressible flow is proposed based on the
three-dimensional spatial velocity increment δ u
i
. The new model is inspired by the structure function formulation developed by Métais and Lesieur [39] and applied in the context of the scale similarity type formulation. First, the similarity between the SGS stress tensor τ
ij
and the velocity increment tensor Q
ij
= δ u
i
δ u
j
is analyzed analytically and numerically using a priori tests of fully developed pipe flow at Re
τ = 180. Both forward and backward energy transfers between resolved and unresolved scales of the flow are well predicted with
a SGS model based on Q
ij
. Secondly, a posteriori tests are performed for two families of turbulent shear flows. LES of fully developed pipe flow up to Re
τ = 520 and LES of round turbulent jet at Re
D
= 25000 carried out with a dynamic version of the model provide promising results that confirm the power of this approach
for wall-bounded and free shear flows. 相似文献
29.
30.