Synthesis of carbamates from carbon dioxide promoted by organostannanes and alkoxysilanes

A cooperative methoxy transfer between orthosilicate esters and organotin oxides was developed for the synthesis of various N ‐alkyl and N ‐aryl carbamates from carbon dioxide in up to 97% isolated yield. The reaction is highly selective and N ‐alkylated amines are not observed. Density functional theory calculations of the reaction were performed and, together with NMR observations, a plausible mechanism featuring the catalytic regeneration of dialkyltin dialkoxide is proposed.     

Quantitative ROESY analysis of computational models: structural studies of citalopram and β‐cyclodextrin complexes by 1H‐NMR and computational methods

Complexation of racemic citalopram with β‐cyclodextrin (β‐CD) in aqueous medium was investigated to determine atom‐accurate structure of the inclusion complexes. ¹H‐NMR chemical shift change data of β‐CD cavity protons in the presence of citalopram confirmed the formation of 1 : 1 inclusion complexes. ROESY spectrum confirmed the presence of aromatic ring in the β‐CD cavity but whether one of the two or both rings was not clear. Molecular mechanics and molecular dynamic calculations showed the entry of fluoro‐ring from wider side of β‐CD cavity as the most favored mode of inclusion. Minimum energy computational models were analyzed for their accuracy in atomic coordinates by comparison of calculated and experimental intermolecular ROESY peak intensities, which were not found in agreement. Several least energy computational models were refined and analyzed till calculated and experimental intensities were compatible. The results demonstrate that computational models of CD complexes need to be analyzed for atom‐accuracy and quantitative ROESY analysis is a promising method. Moreover, the study also validates that the quantitative use of ROESY is feasible even with longer mixing times if peak intensity ratios instead of absolute intensities are used. Copyright © 2015 John Wiley & Sons, Ltd.     

Computational SN2‐Type Mechanism for the Difluoromethylation of Lithium Enolate with Fluoroform through Bimetallic C−F Bond Dual Activation

The reaction mechanism for difluoromethylation of lithium enolates with fluoroform was analyzed computationally (DFT calculations with the artificial force induced reaction (AFIR) method and solvation model based on density (SMD) solvation model (THF)), showing an S_N2‐type carbon–carbon bond formation; the “bimetallic” lithium enolate and lithium trifluoromethyl carbenoid exert the C?F bond “dual” activation, in contrast to the monometallic butterfly‐shaped carbenoid in the Simmons–Smith reaction. Lithium enolates, generated by the reaction of 2 equiv. of lithium hexamethyldisilazide (rather than 1 or 3 equiv.) with the cheap difluoromethylating species fluoroform, are the most useful alkali metal intermediates for the synthesis of pharmaceutically important α‐difluoromethylated carbonyl products.     

Multi‐size‐mesh multi‐time‐step algorithm for noise computation on curvilinear meshes

Aeroacoustic problems are often multi‐scale and a zonal refinement technique is thus desirable to reduce computational effort while preserving low dissipation and low dispersion errors from the numerical scheme. For that purpose, the multi‐size‐mesh multi‐time‐step algorithm of Tam and Kurbatskii [AIAA Journal, 2000, 38 (8), p. 1331–1339] allows changes by a factor of two between adjacent blocks, accompanied by a doubling in the time step. This local time stepping avoids wasting calculation time, which would result from imposing a unique time step dictated by the smallest grid size for explicit time marching. In the present study, the multi‐size‐mesh multi‐time‐step method is extended to general curvilinear grids by using a suitable coordinate transformation and by performing the necessary interpolations directly in the physical space due to multidimensional interpolations combining order constraints and optimization in the wave number space. A particular attention is paid to the properties of the Adams–Bashforth schemes used for time marching. The optimization of the coefficients by minimizing an error in the wave number space rather than satisfying a formal order is shown to be inefficient for Adams–Bashforth schemes. The accuracy of the extended multi‐size‐mesh multi‐time‐step algorithm is first demonstrated for acoustic propagation on a sinusoidal grid and for a computation of laminar trailing edge noise. In the latter test‐case, the mesh doubling is close to the airfoil and the vortical structures are crossing the doubling interface without affecting the quality of the radiated field. The applicability of the algorithm in three dimensions is eventually demonstrated by computing tonal noise from a moderate Reynolds number flow over an airfoil. Copyright © 2013 John Wiley & Sons, Ltd.     

Grown from lithium flux,the ErCo5Si3.17 silicide is a combination of disordered derivatives of the UCo5Si3 and Yb6Co30P19 structure types

A ternary hexaerbium triacontacobalt enneakaidecasilicide, ErCo₅Si_3.17, crystallizes as a combination of disordered variants of the hexagonal UCo₅Si₃ (P6₃/m) and Yb₆Co₃₀P₁₉ (P) structure types and is closely related to the Sc₆Co₃₀Si₁₉ and Ce₆Rh₃₀Si₁₉ types. The Er, Co and three of the Si atoms occupy sites of m.. symmetry and a fourth Si atom occupies a site of .. symmetry. The environment of the Er atom is a 21‐vertex pseudo‐Frank–Kasper polyhedron. Trigonal prismatic coordination is observed for the Si atoms. The Co atoms are enclosed in heavily deformed cuboctahedra and 11‐vertex polyhedra. Crystallochemistry analysis and the data from electronic structure calculations (TB–LMTO–ASA) suggest that the Er atoms form positively charged cations which compensate the negative charge of the [Co₁₂Si₉]^m− polyanions.     

High-accuracy large-step explicit Runge–Kutta (HALE-RK) schemes for computational aeroacoustics

In many realistic calculations, the computational grid spacing required to resolve the mean flow gradients is much smaller than the grid spacing required to resolve the unsteady propagating waves of interest. Because of this, the high temporal resolution provided by existing optimized time marching schemes can be excessive due to the small time step required for stability in regions of clustered grid. In this work, explicit fourth-order accurate Runge–Kutta time marching schemes are optimized to increase the inviscid stability limit rather than the accuracy at large time steps. Single and multiple-step optimized schemes are developed and analyzed. The resulting schemes are validated on several realistic benchmark problems.     

The TV in Your Pocket: Development of Liquid‐Crystal Materials for the New Millennium

New liquid crystals with very low viscosity, good mesophase behavior, and high reliability are necessary to achieve the breakthrough from flat computer monitors to large displays for television. Fluorine plays a decisive role not only because of the polarity it induces in organic molecules but also because of its low polarizability and weak propensity for ion solvation. In addition, subtle stereoelectronic effects in fluorine‐containing liquid crystals influence material properties and allow these to be tuned to some extent to achieve the desired outcome. Some fairly sophisticated chemistry is required that is normally ruled out in the specialty chemicals industry because of cost. The television display market is now entering a phase of saturation. The broad availability of the internet has led to an ever increasing tendency for mobile products. Tablet PCs and smartphones require touch‐panel functionality and low power consumption. New LCD modes with high‐performance liquid crystals and additional components, such as polymerizable materials, can be used in such products.