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1.
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 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
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 β2,3,3‐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. 相似文献
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Rafael López 《Annals of Global Analysis and Geometry》1997,15(3):201-210
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. 相似文献
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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... 相似文献
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C. Foces‐Foces M. Lpez‐Rodríguez C. Prez 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(2):o95-o97
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. 相似文献
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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.
相似文献
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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). 相似文献
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José L. Ló pez Nico M. Temme 《Transactions of the American Mathematical Society》2004,356(11):4323-4342
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.
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