The Regio‐ and Stereoselective Synthesis of trans‐2,3‐Dihydropyridine N‐oxides and Piperidines

Reactivity N? Own : Pyridine N‐oxides can be used for the complete regio‐ and stereoselective synthesis of trans‐substituted piperidines. The sequential addition of Grignard reagents and aldehydes or ketones to pyridine N‐oxides yields a complete regio‐ and stereoselective trans 2,3‐addition reaction in high yields, and the substituted 2,3‐dihydropyridine N‐oxide can be reduced to form 2,3‐trans‐substituted piperidines (see scheme).

     

Interfacial behavior of cubic liquid crystalline nanoparticles at hydrophilic and hydrophobic surfaces

The adsorption behavior of self-assembled lipid liquid crystalline nanoparticles at different model surfaces was investigated in situ by use of ellipsometry. The technique allows time-resolved monitoring of the adsorbed amount and layer thickness under transient and steady-state conditions. The system under study was cubic-phase nanoparticle (CPNP) dispersions of glycerol monooleate stabilized by a nonionic block copolymer, Pluronic F-127. Depending on the surface properties and presence of electrolytes, different adsorption scenarios were discerned: At hydrophilic silica thick surface layers of CPNPs are generated by particle adsorption from dispersions containing added electrolyte, but no adsorption is observed in pure water. Adsorption at the hydrophobic surface involves extensive structural relaxation and formation, which is not electrolyte sensitive, of a classic monolayer structure. The different observations are rationalized in terms of differences in interactions among the CPNP aggregates, their unimer constituents, and the surface and show a strong influence of interfacial interactions on structure formation. Surface self-assembly structures with properties similar to those of the corresponding bulk aggregates appear exclusively in the weak interaction limit. This observation is in agreement with observations for surfactant self-assembly systems, and our findings indicate that this behavior is applicable also to complex self-assembly structures such as the CPNP structures discussed herein.     

Synthesis of multi ring-fused 2-pyridones via an acyl-ketene imine cyclocondensation

[STRUCTURE: SEE TEXT] Polycyclic ring-fused 2-pyridones (5a-e and 9a-e) have been prepared via a microwave-assisted acyl-ketene imine cyclocondensation. Starting from 3,4-dihydroisoquinolines (4a-b) or 3,4-dihydroharman (8), fused 2-pyridones could be prepared in a one-step procedure. By using either Meldrum's acid derivatives (1a-d) or 1,3-dioxine-4-ones (7a-b) as acyl-ketene sources, mono- or disubstitution of the fused 2-pyridone ring could be accomplished. As an application of the method, a formal synthesis of the indole alkaloid sempervilam was performed.     

Photospin-orbit coupling in photonic structures

We show that the inclusion of nonlocality in the constitutive relations in photonic structures has important repercussions in their eigenmode configuration and distribution. In the case of optical activity, the primary manifestation of nonlocality, these features are traced to a photospin-orbit interaction analogous to the electron spin-orbit interaction in asymmetric semiconducting compounds; its impact can be assimilated to that of a magnetic field whose magnitude and direction follow that of the photon quasimomentum, with implications in photospin transport and photospintronics.     

The quiver of projectives in hereditary categories with Serre duality

Let k be an algebraically closed field and A a k-linear hereditary category satisfying Serre duality with no infinite radicals between the preprojective objects. If A is generated by the preprojective objects, then we show that A is derived equivalent to for a so-called strongly locally finite quiver Q. To this end, we introduce light cone distances and round trip distances on quivers which will be used to investigate sections in stable translation quivers of the form ZQ.     

Synthesis of substituted 4-pyridones and 4-aminopyridinium salts via a one-pot pyridine synthesis

Synthesis of substituted 4-benzyloxypyridinium salts by the addition of Grignard reagents to pyridine N-oxides provides an efficient route for obtaining substituted 4-pyridones or 4-aminopyridinium salts.     

Fixed-point algorithms for frequency estimation and structured low rank approximation

We develop fixed-point algorithms for the approximation of structured matrices with rank penalties. In particular we use these fixed-point algorithms for making approximations by sums of exponentials, i.e., frequency estimation. For the basic formulation of the fixed-point algorithm we show that it converges to the solution of a related minimization problem, namely the one obtained by replacing the original objective function with its convex envelope and keeping the structured matrix constraint unchanged.It often happens that this solution agrees with the solution to the original minimization problem, and we provide a simple criterion for when this is true. We also provide more general fixed-point algorithms that can be used to treat the problems of making weighted approximations by sums of exponentials given equally or unequally spaced sampling. We apply the method to the case of missing data, although the above mentioned convergence results do not hold in this case. However, it turns out that the method often gives perfect reconstruction (up to machine precision) in such cases. We also discuss multidimensional extensions, and illustrate how the proposed algorithms can be used to recover sums of exponentials in several variables, but when samples are available only along a curve.