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.     

Surfaces of Constant Mean Curvature Bounded by Two Planar Curves

In this paper we study constant mean curvature compact surfaces with two Jordan curves in parallel planes as boundary and we investigate the point at which the surface inherits the symmetries of its boundary.     

Simultaneous determination of dexamethasone and betamethasone in pharmaceuticals by reversed-phase HPLC

Chromatographia - An HPLC method for the simultaneous determination of the glucocorticoids betamethasone and dexamethasone is described. The method based on the separation of these compounds using...     

A case of concomitant polymorphism and spontaneous resolution: the tetragonal phase of 5‐hydroxymethyl‐7,7,N‐trimethyl‐6‐oxabicyclo[3.2.1]octane‐1‐carboxamide

The title compound, C₁₂H₂₁NO₃, crystallizes in two polymorphic forms, viz. the tetragonal form described here and the monoclinic form described previously [Foces‐Foces, López‐Rodríguez, Pérez, Martín & Pérez‐Hernández (2007). Cryst. Growth Des. 7 , 905–911]. The differences in the conformations of the hydroxymethyl and methylaminocarbonyl substituents have important consequences in the hydrogen‐bond interaction motifs and, therefore, in the packing arrangements. These forms are concomitant polymorphs with melting points differing by 3 K.     

Some results on quasipolyhedral convexity

The objective of this paper is to analyze under what well-known operations the class of quasipolyhedral convex functions, which can be regarded as an extension of that of polyhedral convex functions, is closed. The operations that will be considered are those that preserve polyhedral convexity, such that the image and the inverse image under linear transformations, right scalar multiplication (including the case where λ=0⁺) and pointwise addition.      

Homogeneous quaternionic Kähler structures of linear type

A classification of homogeneous quaternionic Kähler structures by real tensors is given and related to Fino's representation theoretic decomposition. A relationship between the modules whose dimension grows linearly and quaternionic hyperbolic space is found. To cite this article: M. Castrillón López et al., C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Multi-point Taylor expansions of analytic functions

Taylor expansions of analytic functions are considered with respect to several points, allowing confluence of any of them. Cauchy-type formulas are given for coefficients and remainders in the expansions, and the regions of convergence are indicated. It is explained how these expansions can be used in deriving uniform asymptotic expansions of integrals. The method is also used for obtaining Laurent expansions in several points as well as Taylor-Laurent expansions.