Enantioselective Synthesis of Acyclic Stereotriads Featuring Fluorinated Tetrasubstituted Stereocenters

Elaboration of enantioenriched complex acyclic stereotriads represents a challenge for modern synthesis even more when fluorinated tetrasubstituted stereocenters are targeted. We have been able to develop a simple strategy in a sequence of two unprecedented steps combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution. The aldol-Tishchenko reaction directly generates a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter by condensation of fluorinated ketones with aldehydes under very mild basic conditions. The anti 1,3-diols featuring three contiguous stereogenic centers are generated with excellent diastereocontrol (typically >99 : 1 dr). Depending upon the precursors both diastereomers of stereotriads are accessible through this flexible reaction. Furthermore, from the obtained racemic scaffolds, development of an organocatalyzed kinetic resolution enabled to generate the desired enantioenriched stereotriads with excellent selectivity (typically er >95 : 5).     

Two-phase flow in heterogeneous porous media III: Laboratory experiments for flow parallel to a stratified system

Two-phase flow in stratified porous media is a problem of central importance in the study of oil recovery processes. In general, these flows are parallel to the stratifications, and it is this type of flow that we have investigated experimentally and theoretically in this study. The experiments were performed with a two-layer model of a stratified porous medium. The individual strata were composed of Aerolith-10, an artificial: sintered porous medium, and Berea sandstone, a natural porous medium reputed to be relatively homogeneous. Waterflooding experiments were performed in which the saturation field was measured by gamma-ray absorption. Data were obtained at 150 points distributed evenly over a flow domain of 0.1 × 0.6 m. The slabs of Aerolith-10 and Berea sandstone were of equal thickness, i.e. 5 centimeters thick. An intensive experimental study was carried out in order to accurately characterize the individual strata; however, this effort was hampered by both local heterogeneities and large-scale heterogeneities.The theoretical analysis of the waterflooding experiments was based on the method of large-scale averaging and the large-scale closure problem. The latter provides a precise method of discussing the crossflow phenomena, and it illustrates exactly how the crossflow influences the theoretical prediction of the large-scale permeability tensor. The theoretical analysis was restricted to the quasi-static theory of Quintard and Whitaker (1988), however, the dynamic effects described in Part I (Quintard and Whitaker 1990a) are discussed in terms of their influence on the crossflow.Roman Letters A interfacial area between the -region and the -region contained within V, m² - a vector that maps onto , m - b vector that maps onto , m - b vector that maps onto , m - B second order tensor that maps onto , m² - C second order tensor that maps onto , m² - E energy of the gamma emitter, keV - f fractional flow of the -phase - g gravitational vector, m/s² - h characteristic length of the large-scale averaging volume, m - H height of the stratified porous medium , m - i unit base vector in the x-direction - K local volume-averaged single-phase permeability, m² - K - {K}, large-scale spatial deviation permeability - { K} large-scale volume-averaged single-phase permeability, m² - K ^* large-scale single-phase permeability, m² - K ^** equivalent large-scale single-phase permeability, m² - K local volume-averaged -phase permeability in the -region, m² - K local volume-averaged -phase permeability in the -region, m² - K - {K } , large-scale spatial deviation for the -phase permeability, m² - K ^* large-scale permeability for the -phase, m² - l thickness of the porous medium, m - l characteristic length for the -region, m - l characteristic length for the -region, m - L length of the experimental porous medium, m - characteristic length for large-scale averaged quantities, m - n outward unit normal vector for the -region - n outward unit normal vector for the -region - n unit normal vector pointing from the -region toward the -region (n = - n ) - N number of photons - p pressure in the -phase, N/m² - p ₀ reference pressure in the -phase, N/m² - local volume-averaged intrinsic phase average pressure in the -phase, N/m² - large-scale volume-averaged pressure of the -phase, N/m² - large-scale intrinsic phase average pressure in the capillary region of the -phase, N/m² - - , large-scale spatial deviation for the -phase pressure, N/m² - p_c , capillary pressure, N/m² - p _c capillary pressure in the -region, N/m² - p capillary pressure in the -region, N/m² - {p _c } ^c large-scale capillary pressure, N/m² - q -phase velocity at the entrance of the porous medium, m/s - q -phase velocity at the entrance of the porous medium, m/s - S_wi irreducible water saturation - S /, local volume-averaged saturation for the -phase - S _i initial saturation for the -phase - S _r residual saturation for the -phase - S ^* { }^*/}^*, large-scale average saturation for the -phase - S saturation for the -phase in the -region - S saturation for the -phase in the -region - t time, s - v -phase velocity vector, m/s - v local volume-averaged phase average velocity for the -phase, m/s - {v } large-scale averaged velocity for the -phase, m/s - v local volume-averaged phase average velocity for the -phase in the -region, m/s - v local volume-averaged phase average velocity for the -phase in the -region, m/s - v -{v } , large-scale spatial deviation for the -phase velocity, m/s - v -{v } , large-scale spatial deviation for the -phase velocity in the -region, m/s - v -{v } , large-scale spatial deviation for the -phase velocity in the -region, m/s - V large-scale averaging volume, m³ - y position vector relative to the centroid of the large-scale averaging volume, m - {y}^c large-scale average of y over the capillary region, m Greek Letters local porosity - local porosity in the -region - local porosity in the -region - local volume fraction for the -phase - local volume fraction for the -phase in the -region - local volume fraction for the -phase in the -region - {}^* { }^*+{ }^*, large-scale spatial average volume fraction - { }^* large-scale spatial average volume fraction for the -phase - mass density of the -phase, kg/m³ - mass density of the -phase, kg/m³ - viscosity of the -phase, N s/m² - viscosity of the -phase, Ns/m² - V /V , volume fraction of the -region ( + =1) - V /V , volume fraction of the -region ( + =1) - attenuation coefficient to gamma-rays, m^-1 - -      

Diffusion in isotropic and anisotropic porous systems: Three-dimensional calculations

Effective diffusion coefficients were calculated numerically for three-dimensional unit cells representative of different unconsolidated porous media. These numerical results were compared with the experimental results of Kim for packed beds of glass spheres, mica particles, and an artificial porous medium composed of mylar disks. These three-dimensional numerical results confirm that the porosity is the essential parameter for the determination of the effective diffusion coefficient in the case of unconsolidated isotropic systems. In the case of anisotropic systems, better agreement is obtained between numerical predictions and actual data when the unit cell is three-dimensional rather than twodimensional. This emphasizes the fact that three-dimensional unit cells feature more realistic geometrical properties which are needed to accurately describe anisotropic systems.     

Metallation des halogenures d'aryle par le tributylstannyllithium dans le tetrahydrofuranne

The metallation of aryl halides with tributylstannyllithium in THF proceeds via at least three different mechanisms whose relative rates depend on the nature of the halogen, the substrate and the experimental conditions. In the case of aryl bromides, a halogenmetal exchange (major process) is competing with a radical mechanism. With aryl chlorides, an arynic process, a halogenmetal exchange and a radical mechanism are involved. Finally, with aryl fluorides, the arynic process is usual, but it may be strongly competed by a radical mechanism whenever suitable experimental conditions are arranged.     

Preliminary study of some “pyro”-silico-nitrides

Two oxynitrides of the LnSiDN system were studied by IR spectroscopy : Nd₂Si₃O₃N₄, with a melilite-like structure and Nd₄Si₂O₇N₂ with a cuspidine-like structure. The first compound belongs to the space group D³_2d(P4̄2₁m) with two formula units per unit cell. There are 10 vibrations of B₂ species and 18 of E species active in the IR. A preliminary study by neutron diffraction displayed that the oxygen and nitrogen atoms are perfectly ordered, and that two silicon atoms are bridged by an oxygen. In the present work, we compare the (SiON₂)₂O IR vibrations with those of silicon oxynitride previously studied and |Si₂O₇|^6? ion in akermanite. The space group of cuspidine is C⁵_2h (P2₁/c with 4 formula units per unit cell. So, 21 vibrations of A_u species and 21 of B_u species are active in IR absorption for Nd₄Si₂O₇N₂. The absorption bands are not as sharp as the bands in Nd₂Si₃O₃N₄. This fact might be explained by a disordered structure as the nitrogen position has not been exactly determined.     

Syntheses of Theaspirone and Vitispirane via Palladium(II)-Catalyzed Oxaspirocyclization

Total syntheses of theaspirone (A and B) and vitispirane (A and B) are described. The key step in the syntheses is the palladium(II)-catalyzed intramolecular oxaspirocyclization of diene alcohol 4 to either vitispirane or the allylic alcohol 9. The outcome of the oxaspirocyclization is very much dependent on the solvent employed. In water-acetic acid (4:1) a 1:1 mixture of the diastereomeric alcohols 9A and 9B was exclusively formed. In water with 8 equiv of a strong non-nucleophilic acid, vitispiranes A and B (1:1) were obtained. An alternative procedure to obtain vitispirane with the use of LiCl and K(2)CO(3) is described. In the latter reaction vitispirane B is formed preferentially. This result is explained by an equilibrium between the two possible pi-allyl complexes 5A and 5B, the kinetically favored 5B being transformed into vitispirane 3B before isomerization to 5A occurs.     

Dispersion in Heterogeneous Porous Media: One-Equation Non-equilibrium Model

In this paper, the method of large-scale averaging is used to develop two different one-equation models describing dispersion in heterogeneous porous media. The first model represents the case of large-scale mass equilibrium, while the second represents the asymptotic behavior of a two-equation model obtained by large-scale averaging. It is shown that a one-equation, non-equilibrium model can be developed even when the intrinsic large-scale averaged concentrations for each region are not equal. The solution of this non-equilibrium model is equivalent to the asymptotic behavior of the two-equation model.     

Electrochemical cleavage of sulfonamides: an efficient and tunable strategy to prevent β-fragmentation and epimerization

The electrochemical reduction of sensitive sulfonamides is described. The addition of a benzoyl group on the nitrogen atom facilitates the reductive cleavage of sulfonamides preventing β-fragmentation and epimerization. This strategy was successfully applied to the cyclopropylamine and to α-amino stannanes.     

Determination of Chlorinated Solvent Sorption by Porous Material—Application to Trichloroethene Vapor on Cement Mortar

Experiments have been performed to investigate the sorption of trichloroethene (TCE) vapor by concrete material or, more specifically, the cement mortar component. Gas-flow experiments were conducted using columns packed with small pieces of cement mortar obtained from the grinding of typical concrete material. Transport and retardation of TCE at high vapor concentrations (500 mg L \(^{-1})\) was compared to that of a non-reactive gas tracer (Sulfur Hexafluoride, SF \(_{6})\) . The results show a large magnitude of retardation (retardation factor \(=\) 23) and sorption (sorption coefficient \(=\) 10.6 cm \(^{3}\)  g \(^{-1})\) for TCE, compared to negligible sorption for SF \(_{6}\) . This magnitude of sorption obtained with pollutant vapor is much bigger than the one obtained for aqueous-flow experiments conducted for water-saturated systems. The considerable sorption exhibited for TCE under vapor-flow conditions is attributed to some combination of accumulation at the air-water interface and vapor-phase adsorption, both of which are anticipated to be significant for this system given the large surface area associated with the cement mortar. Transport of both SF \(_{6}\) and TCE was simulated successfully with a two-region physical non-equilibrium model, consistent with the dual-medium structure of the crushed cement mortar. This work emphasizes the importance of taking into account sorption phenomena when modeling transport of volatile organic compounds through concrete material, especially in regard to assessing vapor intrusion.