Ring-closing metathesis of sulfoximine-substituted N-tethered trienes: modular asymmetric synthesis of medium-ring nitrogen heterocycles

A synthesis of sulfoximine-substituted medium-ring nitrogen heterocycles (MRNHs) having a high degree of substitution has been developed. Its key steps are the modular asymmetric synthesis of sulfoximine-substituted N-tethered trienes and their Ru-catalyzed ring-closing metathesis (RCM) reaction. The highly substituted N-tethered trienes were obtained enantio- and diastereopure through 1) the diastereoselective aminoalkylation of sulfoximine-substituted allyltitanium complexes with N-tert-butylsulfonyliminoester, 2) N-allylation of homoallylic N-sulfonyl amines, 3) allylation, hydroxylalkylation, and formylation of α-lithioalkenylsulfoximines, and 4) allylation of α-formylalkenylsulfoximines. The Ru-catalyzed RCM reaction of the sulfoximine-substituted 1,7,10- and 1,7,12-trienes stereoselectively afforded the corresponding nine-, ten-, and eleven-membered MRNHs in good yields. An interesting difference in reactivity was noted in the case of a sulfoximine-substituted 1,7,10-triene and its corresponding 1,10-diene. While the triene readily underwent a RCM reaction, the diene reacted only in the presence of Ti(OiPr)(4) under formation of the corresponding MRNH. The feasibility of a removal of the sulfoximine auxiliary and the N-sulfonyl protecting group from the MRNHs were demonstrated through reduction and cleavage, respectively, of a nine-membered heterocycle, both of which proceeded readily and gave the corresponding cyclic alkene and amine, respectively.     

Performance evaluation of numerical methods for the Maxwell–Liouville–von Neumann equations

The Maxwell–Liouville–von Neumann (MLN) equations are a valuable tool in nonlinear optics in general and to model quantum cascade lasers in particular. Several numerical methods to solve these equations with different accuracy and computational complexity have been proposed in related literature. We present an open-source framework for solving the MLN equations and parallel implementations of three numerical methods using OpenMP. The performance measurements demonstrate the efficiency of the parallelization.     

Catalyst Deactivation During Rhodium Complex-Catalyzed Propargylic C−H Activation

Detailed mechanistic investigations on our previously reported synthesis of branched allylic esters by the rhodium complex-catalyzed propargylic C−H activation have been carried out. Based on initial mechanistic studies, we present herein more detailed investigations of the reaction mechanism. For this, various analytical (NMR, X-ray crystal structure analysis, Raman) and kinetic methods were used to characterize the formation of intermediates under the reaction conditions. The knowledge obtained by this was used to further optimize the previous conditions and generate a more active catalytic system.     

The net distribution of elements in multiphase polymer materials via element-specific electron microscopy

Applications of the Electron Spectroscopic Imaging technique (ESI) within the field of multiphase polymer materials are discussed. Imaging with elastically scattered electrons as well as imaging with electrons with defined energy loss are presented. From the latter the net distribution of elements can be derived. Several examples are given: Glassy diblock copolymers polystyrene-block-poly(2-vinyl pyridine), polyethylenes, interpenetrating networks, interdiffusion couples, blends of polystyrene and polystyrene-graft-poly(oxyethylene), carbon black reinforced natural rubber, and epitactic growth of poly(1-pentenylene) on isotactic poly (propylene) surface. Visualization of the rigid amorphous phase in polyethylene is presented, as well as electron spectroscopic diffraction (ESD) of oriented PE. One of the features of ESI is due to the fact that discrimination between true morphology and artefacts is possible in an unbiased manner, even for minor details: Heavy metal staining is abandonable, and structural analysis by one element may be proved by analysis with other elements, which may be present in the sample or which may be added by chemical reaction or interaction with groups within the molecules.