Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.     

Experimental Investigations on the Thermal Diffusion Characteristics and Photoluminescence in Multiphase Micro Fluids Containing ZnO Micro Tubes and Fluorescein Dye

Optics and Spectroscopy - Scattering of light by disordered structures is normally detrimental to their applicability in many optoelectronic devices. However, some micro and nanostructures are...     

Invariant discrete flows

In this paper, we investigate the evolution of joint invariants under invariant geometric flows using the theory of equivariant moving frames and the induced invariant discrete variational complex. For certain arc length preserving planar curve flows invariant under the special Euclidean group , the special linear group , and the semidirect group , we find that the induced evolution of the discrete curvature satisfies the differential‐difference mKdV, KdV, and Burgers' equations, respectively. These three equations are completely integrable, and we show that a recursion operator can be constructed by precomposing the characteristic operator of the curvature by a certain invariant difference operator. Finally, we derive the constraint for the integrability of the discrete curvature evolution to lift to the evolution of the discrete curve itself.     

Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

Compatible relations on filters and stability of local topological properties under supremum and product

An abstract scheme using particular types of relations on filters leads to general unifying results on stability under supremum and product of local topological properties. We present applications for Fréchetness, strong Fréchetness, countable tightness and countable fan-tightness, some of which recover or refine classical results, some of which are new. The reader may find other applications as well.     

Determination of lithium in wines by atomic absorption spectrometry

Lithium (10–150 ng ml^?1) in wine is determined by atomic absorption spectrometry by direct nebulization and after digestion with mixed acids. The results of methods are similar. Thirty-four wines from various Spanish provinces are analysed.