Tandem enantioselective conjugate addition--cyclopropanation. Application to natural products synthesis

A tandem asymmetric conjugate addition-cyclopropanation was developed, in which a cyclic or linear enone was converted to a TMS-protected 3-substituted-cyclopropanol in an efficient one-pot reaction. These compounds were then selectively cleaved to yield alpha-methyl-beta-alkyl ketones, alpha-methylene-enones, or chain extended gamma-alkyl-enones. This methodology was applied to the formal total synthesis of (-)-(S,S)-clavukerin A and (+)-(R,S)-isoclavukerin.     

Transition-metal nanoparticles in imidazolium ionic liquids: recyclable catalysts for biphasic hydrogenation reactions

1-n-Butyl-3-methylimidazolium hexafluorophosphate room-temperature ionic liquid is not only suitable as a medium for the preparation and stabilization of iridium nanoparticles but also ideal for the generation of recyclable biphasic catalytic systems for hydrogenation reactions. Thus, Ir(0) nanoparticles with a mean diameter of 2 nm have been prepared by reduction of Ir(I) dissolved in the ionic liquid with H2. This catalytic solution can be reused several times for the biphasic hydrogenation of olefins under mild reaction conditions.     

Regularity of CR maps between convex hypersurfaces of finite type

We study rigidity and regularity properties of CR maps between smooth convex hypersurfaces of finite type in

     

Effect of aerosil dispersions on the nematic-to-isotropic interface

The effect of silica aerosils on the kinetics of the first-order nematic-isotropic (NI) phase transition is phenomenologically described in the framework of the time-dependent Landau-Ginzburg equation. A steady-state solution to the equation is presented such that the NI interface may propagate with a solitary-like wave profile under constant quenching. The results provide a plausible basis for the interpretation of the dynamical effects of quenched disorder in the liquid-crystal systems, caused by randomly interconnected porous media, such as aerosils. In the low silica aerosil ρ_s ( ≤0.1 g/cm^3) regime, the calculated values of the interface velocity v(T,ρ_s), the interface thickness κ(T,ρ_s), and the critical radius of a spherical nucleus of new nematic phase in a bulk isotropic environment, composed of polar molecules, such as 4-n-octyl- 4^′- cyanobiphenyl and 4-n-heptyl- 4^′- cyanobiphenyl shows that the effect of silica aerosils on the kinetics is reflected in a shifting of the set of temperature-dependent curves to lower temperature values.-1     

Nucleophilic addition to 3-substituted pyridinium salts: expedient syntheses of (-)-L-733,061 and (-)-CP-99,994

[reaction: see text] The addition of nucleophiles to 3-substituted pyridinium salts prepared from N-methylbenzamide and various pyridines has been investigated. Good to excellent regioselectivities favoring the 2,3-disubstituted 1,2-dihydropyridines were observed. The resulting 1,2-dihydropyridines led to the corresponding 2,3-disubstituted pyridines upon treatment with Mn(OAc)3/NaIO4. This methodology was also successfully applied to the enantioselective syntheses of (-)-L-733,061 and (-)-CP-99,994, two members of a new class of highly potent, nonpeptide, Substance P antagonists.     

Multiple and Polynomial Recurrence for Abelian Actions in Infinite Measure

The (C,F)-construction from a previous paper of the first authoris applied to produce a number of funny rank one infinite measurepreserving actions of discrete countable Abelian groups G with‘unusual’ multiple recurrence properties. In particular,the following are constructed for each p N{}:

1. a p-recurrent actionT=(T_g)_gG such that (if p) no one transformationT_g is (p+1)-recurrentfor every element g of infinite order;
2. an action T=(T_g)_gGsuch that for every finite sequence g1,...,g_rGwithout torsionthe transformation T_g1x...x T_gr is ergodic,p-recurrent but(if p) not (p+1)-recurrent;
3. a p-polynomially recurrent (C,F)-transformationwhich (if p)is not (p+1)-recurrent.

-recurrence here meansmultiple recurrence. Moreover, it is shown that there existsa (C,F)-transformation which is rigid (and hence multiply recurrent)but not polynomially recurrent. Nevertheless, the subset ofpolynomially recurrent transformations is generic in the groupof infinite measure preserving transformations endowed withthe weak topology.     

Contact dynamics in a gently vibrated granular pile

We use multispeckle diffusive wave spectroscopy to probe the micron-scale dynamics of a water-saturated granular pile submitted to discrete gentle taps. The typical time scale between plastic events is found to increase dramatically with the number of applied taps. Furthermore, this microscopic dynamics weakly depends on the solid fraction of the sample. This process is largely analogous to the aging phenomenon observed in thermal glassy systems. We propose a heuristic model where this slowing-down mechanism is associated with a slow evolution of the distribution of the contact forces between particles. This model accounts for the main features of the observed dynamics.     

Simultaneous achievement of polarization attraction and Raman amplification in isotropic optical fibers

We present a theoretical analysis and experimental demonstration of the combined effects of polarization attraction and Raman amplification in isotropic optical fibers. The polarization attraction process is based on four-wave mixing interaction of counterpropagating pump and signal waves. We show that this technique can be used for the design of a highly efficient nonlinear system that permits the simultaneous processing of repolarization and amplification of light waves in dielectric media.