Chiral alpha-branched benzylic carbocations: diastereoselective intermolecular reactions with arene nucleophiles and NMR spectroscopic studies

The chiral benzylic alcohols 1-6 were prepared and subjected to S(N)1-type displacement reactions with various arene nucleophiles in acidic medium. Under optimized conditions (HBF(4).OEt(2), CH(2)Cl(2), -78 degrees C --> r.t.) the corresponding 1,1-diarylalkanes 11-18 and 20 were obtained in good chemical yields (48-99%). The facial diastereoselectivity of the reaction is high (d.r. = 91/9-97/3) when the substrate bears a stereogenic carbon center -CHtBuMe in the alpha-position to the electrophilic carbon atom. If the starting material was enantiomerically pure, no significant racemization was observed (94% ee --> 92% ee). The reactions proceed stereoconvergently as demonstrated by the conversion of the separated diastereoisomers syn-1a and anti-1a in separate reactions to the same product syn-11 (d.r. = 97/3). Further evidence for long-lived chiral benzylic carbocations as reaction intermediates was obtained from NMR studies in superacidic medium. The chiral cation 24 was generated in SO(2)ClF as the solvent at -70 degrees C employing SbF(5) as the Lewis acid and characterized by its (1)H and (13)C NMR spectra. NOE measurements suggest a preferred conformation in which the diastereotopic faces of the cation are differentiated by the two carbon substituents R and Me at the stereogenic carbon center in the alpha-position. The hypothesis is further supported by the observation that the diastereoselectivity of the substitution reaction decreases if the bulky tert-butyl (R = tBu) substituent in the substrate 1a is replaced by a smaller ethyl group (2a, R = Et).     

Environmentally induced quantum dynamical phase transition in the spin swapping operation

Quantum information processing relies on coherent quantum dynamics for a precise control of its basic operations. A swapping gate in a two-spin system exchanges the degenerate states |(up arrow, down arrow)> and |(down arrow, up arrow)>. In NMR, this is achieved turning on and off the spin-spin interaction b=DeltaE that splits the energy levels and induces an oscillation with a natural frequency DeltaE/Planck's. Interaction of strength Planck's/tau(SE), with an environment of neighboring spins, degrades this oscillation within a decoherence time scale tau(phi). While the experimental frequency omega and decoherence time tau(phi) were expected to be roughly proportional to b/Planck's and tau(SE), respectively, we present here experiments that show drastic deviations in both omega and tau(phi). By solving the many spin dynamics, we prove that the swapping regime is restricted to DeltaEtau(SE) similar or greater than Planck's. Beyond a critical interaction with the environment the swapping freezes and the decoherence rate drops as 1/tau(phi) proportional to (b/Planck's)2tau(SE). The transition between quantum dynamical phases occurs when omega proportional to sqrt (b/Planck's)2-(k/tau(SE)2 becomes imaginary, resembling an overdamped classical oscillator. Here, 0< or =k2< or =1 depends only on the anisotropy of the system-environment interaction, being 0 for isotropic and 1 for XY interactions. This critical onset of a phase dominated by the quantum Zeno effect opens up new opportunities for controlling quantum dynamics.     

Synthesis of (-)-stemoamide using a stereoselective anti-aldol step

The synthesis of (-)-stemoamide was achieved in 11 steps from 5-acetoxy-N-crotyl pyrrolidinone. A chiral N-acyl thiazolidinethione was employed in a stereoselective addition to a cyclic N-acyl iminium ion to install the required stereochemistry of carbon C9a. This iminium ion addition product was employed in a stereoselective MgBr2-catalyzed anti-aldol reaction to install the required stereochemistry of carbons C8 and C9. The X-ray crystal analysis of (-)-stemoamide confirmed the structure and the stereochemical outcome of these selective reactions.     

Effects of Large Scales Motion in Unstable Stratified Shear Flows

Homogeneous turbulence under unstable uniform stratification (N ² < 0) and vertical shear is investigated by using the linear theory (or the so-called rapid distortion theory, RDT) for an initial isotropic turbulence over a range −∞ ≤ R _i =N ²/S ² ≤ 0. The initial potential energy is zero and P _r =1 (i.e. the molecular Prandtl number).One-dimensional (streamwise) k ₁−spectra, especially Θ₃₃(k ₁) (i.e., that of the vertical kinetic energy, are investigated. In agreement with previous experiments, it is found that the unstable stratification affects the turbulence quantities at all scales. A significant increase of the vertical kinetic energy is observed at low wavenumbers k ₁ (i.e. large scales) due to an increase of the stratification . The effect of the shear (S) is appreciable only at high wavenumbers k ₁ (i.e. small scales).Based on the importance of the spectral components with k ₁ = 0, the asymptotic forms of Θ _ij (k ₁ = 0) or equivalently the so-called “two-dimensional” energy components (2DEC) are analyzed in detail. The asymptotic form for the ratio of 2DEC is compared to the long-time limit of the ratio of real energies. In the unstable stratified shearless case (S=0,N ² ≠ 0) the variances and the covariances of the velocity and the density are derived analytically in terms of the Weber functions, while when S ≠ 0 and N ² ≠ 0 they are obtained numerically (−100 ≤ R _i <0 and . The results are discussed in connection to previous experimental results in unstable stratified open channel flows cooled from above by Komori et al. Phy Fluids 25, 1539–1546 (1982).It is shown that the Richardson number dependence of the long-time limit of the ratios of real energies is well described by this “simple” model (i.e. the dependence of the long-time limit of 2DEC on R _i ). For example, the ratio of the potential energy to the kinetic energy (q ²/2), approaches −R _i /(1−R _i ), the ratio of turbulent energy production by buoyancy forces to production by shearing forces (i.e. the flux Richardson number, R _if ), approaches R _i . Also, the Richardson number dependence of the principal angle (β) of the Reynolds stress tensor and the angle (β_ρ) of the scalar flux vector is fairly predicted by this model .On the other hand, it is found that the above ratios are insensitive to viscosity, while the ratios ɛ /q ² and , depend on the viscosity and they evolve asymptotically like t ⁻¹. The turbulent Froude number, F _rt =(L _Oz /L _E )^2/3, where L _Oz and L _E are the Ozmidov length scale and the Ellison length scale, respectively, evolves asymptotically like t ^−1/3.     

Particle-yield modification in jetlike azimuthal dihadron correlations in Pb-Pb collisions at √s(NN)=2.76 TeV

The yield of charged particles associated with high-p(t) trigger particles (83 GeV/c on the away side drops to about 60% of that observed in pp collisions, while on the near side a moderate enhancement of 20%-30% is found.     

Data mining usage in Italian SMEs: an integrated SEM-ANN approach

Central European Journal of Operations Research - Data mining is the process of knowledge extraction from the data with the algorithms that identify hidden relationships and patterns, which are...     

Principled analyses and design of first-order methods with inexact proximal operators

Mathematical Programming - Proximal operations are among the most common primitives appearing in both practical and theoretical (or high-level) optimization methods. This basic operation typically...     

Stability of a steady flow guided by flexible walls

Flexible channels conveying fluid may loose stability by divergence or flutter, thus leading to undesirable dynamic behaviour. A lot of investigations have already been done on this subject, each involving structural models expressing a specific type of stiffness. The aim of this contribution is to investigate and compare systematically the influence of various types of structural stiffness on the stability behaviour of the coupled problem. Therefore, a simple, yet general model is built. The fluid is bounded by a rigid and an elastical supported, flexible wall, which exhibits bending and extensional stiffness and considers effects of pre-load. The influence of the various characteristics on the stability of the steady state is discussed and a perturbation approach is used to investigate the influence of small nonlinearities. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoresponsive liquid crystalline and amorphous polymers

Isomerization processes of azobenzene dyes dissolved in a glassy polymeric matrix or attached in glassy amorphous or liquid crystalline polymers to the backbone as side groups are induced by light. The isomerization process, in turn, causes the dye to reorient provided that polarized light is used: the long axis of the dye is oriented perpendicular to the polarization direction in the stationary case. Such a reorientation gives rise to strong modifications of the optical properties. This contribution is concerned with the analysis of the correlation between the nature of the azobenzene dyes, the isomerization, reorientation and modulations discussed above and with possible applications in the optical holographic storage. Considered are, in particular, dye/matrix combinations giving rise to nonlinear holographic responses, two photon holography, transient holographic modes applicable for holographic displays and the optical switching of other than optical properties.