New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Pattern formation and competition in photorefractive oscillators

We introduce a general model of pattern formation in optical systems made of a cavity with an active medium as a photorefractive crystal fed by a pump. The model is based on the interplay of a diffractive equation for the optical field and a diffusive equation for the medium refractivity. The aim of the model is to describe a series of experiments which have shown mode competition (periodic or chaotic alternation) for low Fresnel numbers (F) and mode coexistence, leading to short range space correlations, for high F. For low F, a linear stability analysis provides the set of modes above threshold as a function of the transverse wave number. Due to the interplay of the optical and the diffusive interactions, different behaviors result depending on the thickness of the medium as compared to the optical absorption length and diffusion length. Including the leading nonlinearities compatible with the symmetry constraints, we introduce normal form equations which describe the time-dependent mode competition. In the case of a large number of modes (high F), nonlinear mode-mode interaction is equivalent to a self-induced noise. In this limit, the relevant feature to be compared with the experiment is the power spectrum.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Effect of viscous dissipation on the mixed convection heat transfer from an exponentially stretching surface

The mixed convection flow and heat transfer from an exponentially stretching vertical surface in a quiescent fluid is analyzed using similarity solution technique. Wall temperature and stretching velocity are assumed to have specific exponential function forms. The influence of buoyancy along with viscous dissipation on the convective transport in the boundary layer region is analyzed in both aiding and opposing flow situations. The flow is governed by the mixed convection parameter Gr/Re². The velocity and temperature inside the boundary layer are observed to be influenced by the parameters like Prandtl number Pr, Gebhart number Gb. Significant changes are observed in non-dimensional skin friction and heat transfer coefficients due to viscous dissipation in the medium. The flow and temperature distributions inside the boundary layer are analyzed and the results for non-dimensional skin friction and heat transfer coefficients are discussed through computer generated plots.     

Deterministic chaos in laser with injected signal

Dynamic behaviour of an homogeneously broadened laser with injected signal is analyzed for a model in which the polarization is adiabatically eliminated. Detuning between the atomic resonant frequency, the cavity resonance and the frequency of the external signal is considered. We show that a transition to chaos via intermittency is possible for parameters appropriate for CO₂ lasers.     

Onset of Lasing in Small Devices: The Identification of the First Threshold through Autocorrelation Resonance

A simple technique for identifying the onset of coherent emission in mesoscale lasers, which makes use of a small‐amplitude modulation added to the pump, is introduced. The optimal modulation frequency is obtained from the radio‐frequency power spectrum of the unperturbed laser emission. The identification of the lasing onset rests on the appearance of a resonance in the experimentally measured zero‐order autocorrelation function (g⁽²⁾(0)) plotted as a function of the pump rate. Numerical proof is provided in support of the autocorrelation resonance. The intrinsic simplicity of this technique and its inherent compatibility with photon counting makes it an excellent tool for certifying the onset of laser emission independent of the laser cavity volume. Recently published measurements of g⁽²⁾(0), obtained in nanolasers, support the extension of this technique to nanoscale devices.