Asymmetric Synthesis of Densely Functionalized Medium‐Ring Carbocycles and Lactones through Modular Assembly and Ring‐Closing Metathesis of Sulfoximine‐Substituted Trienes and Dienynes

An asymmetric synthesis of densely functionalized 7–11‐membered carbocycles and 9–11‐membered lactones has been developed. Its key steps are a modular assembly of sulfoximine‐substituted C‐ and O‐tethered trienes and C‐tethered dienynes and their Ru‐catalyzed ring‐closing diene and enyne metathesis (RCDEM and RCEYM). The synthesis of the C‐tethered trienes and dienynes includes the following steps: 1) hydroxyalkylation of enantiomerically pure titanated allylic sulfoximines with unsaturated aldehydes, 2) α‐lithiation of alkenylsulfoximines, 3) alkylation, hydroxy‐alkylation, formylation, and acylation of α‐lithioalkenylsulfoximines, and 4) addition of Grignard reagents to α‐formyl(acyl)alkenylsulfoximines. The sulfoximine group provided for high asymmetric induction in steps 1) and 4). RCDEM of the sulfoximine‐substituted trienes with the second‐generation Ru catalyst stereoselectively afforded the corresponding functionalized 7–11‐membered carbocyles. RCDEM of diastereomeric silyloxy‐substituted 1,6,12‐trienes revealed an interesting difference in reactivity. While the (R)‐diastereomer gave the 11‐membered carbocyle, the (S)‐diastereomer delivered in a cascade of cross metathesis and RCDEM 22‐membered macrocycles. RCDEM of cyclic trienes furnished bicyclic carbocycles with a bicyclo[7.4.0]tridecane and bicyclo[9.4.0]pentadecane skeleton. Selective transformations of the sulfoximine‐ and bissilyloxy‐substituted carbocycles were performed including deprotection, cross‐coupling reaction and reduction of the sulfoximine moiety. Esterification of a sulfoximine‐substituted homoallylic alcohol with unsaturated carboxylic acids gave the O‐tethered trienes, RCDEM of which yielded the sulfoximine‐substituted 9–11‐membered lactones. RCEYM of a sulfoximine‐substituted 1,7‐dien‐10‐yne showed an unprecedented dichotomy in ring formation depending on the Ru catalyst. While the second‐generation Ru catalyst gave the 9‐membered exo 1,3‐dienyl carbocycle, the first‐generation Ru catalyst furnished a truncated 9‐membered 1,3‐dieny carbocycle having one CH₂ unit less than the dienyne.     

Neutron self-shielding in irradiation channels of small reactors is isotropic

In order to predict the self-shielding effect in neutron activation of non-spherical samples in reactor neutron spectra, it is important to know whether the neutron field is sufficiently anisotropic to cause significant variations between horizontal and vertical sample orientation or with orientation relative to the direction towards the reactor core. Metal wires with significant neutron self-shielding were irradiated in several channels of the SLOWPOKE reactor at Ecole Polytechnique Montreal and the TRIGA reactor at the Jožef Stefan Institute. In all cases, the amount of thermal or epithermal self-shielding was found to be identical, within the experimental uncertainty, regardless of the orientation of the wire, indicating that the neutron field is essentially isotropic. Models used to predict neutron self-shielding need to be adjusted accordingly. In our Monte Carlo model, the tube-shaped neutron source was moved back into the moderator and reflecting materials near the sample location were included, which produced an isotropic neutron field at the sample location.     

Edge singularities and structure of the 3-D Williams expansion

The elastic solution in a vicinity of a re-entrant wedge can be described by a Williams like expansion in terms of powers of the distance to a point on the edge. This expansion has a particular structure due to the invariance of the problem by translation parallel to the edge. We show here that some terms, so-called primary solutions, derive directly from solutions to the 2-D corner problem posed in the orthogonal cross section of the domain. The others, baptized shadow functions, derive of the primary solutions by integration along the axis parallel to the edge. This 3-D Williams expansion is shown to be equivalent to the edge expansion proposed by Costabel et al. [M. Costabel, M. Dauge, Z. Yosibash, A quasidual function method for extracting edge stress intensity functions, SIAM J. Math. Anal. 35 (5) (2004) 1177–1202]. To cite this article: T. Apel et al., C. R. Mecanique 336 (2008).     

Stimuli-Responsive Particle-Based Amphiphiles as Active Colloids Prepared by Anisotropic Click Chemistry

Amphiphiles alter the energy of surfaces, but the extent of this feature is typically constant. Smart systems with amphiphilicity as a function of an external, physical trigger are desirable. As a trigger, the exposure to a magnetic field, in particular, is attractive because it is not shielded in water. Amphiphiles like surfactants are well known, but the magnetic response of molecules is typically weak. Vice-versa, magnetic particles with strong response to magnetic triggers are fully established in nanoscience, but they are not amphiphilic. In this work colloids with Janus architecture and ultra-small dimensions (25 nm) have been prepared by spatial control over the thiol-yne click modification of organosilica-magnetite core–shell nanoparticles. The amphiphilic properties of these anisotropically modified particles are proven. Finally, a pronounced and reversible change in interfacial stabilization results from the application of a weak (<1 T) magnetic field.     

Magnetic field effects on the optical properties of an azo-dye doped liquid crystal

Homeotropically aligned nematic liquid crystals doped with azo-dye were subjected both to a linear polarized light of a He–Ne laser and to a magnetic field perpendicular to the incident light beam. We found that the emerging light was elliptically polarized when using magnetic field strengths higher than the threshold value for the magnetic Freedericksz transition. The light transmission, the rotatory power (induced by azo-dye) and the ellipticity varied quasiperiodically when increasing magnetic field strength. The number and positions of maxima and minima depend on the cell thicknesses. Changes in the phase difference between the emergent ordinary and extraordinary rays were computed from the experimental data and the magnetic field dependence of the birefringence was determined.