La caminería en al-Andalus (ss. VIII-XV J.C.): consideraciones metodológicas, históricas y administrativas para su estudio

Este estudio es una síntesis de las últimas aportaciones acerca de las vías en al-Andalus (ss. VIII-XV), cuya estructura inicial es herencia de la época romana. Dadas las limitaciones que imponen los escasos datos que hallamos en las fuentes árabes y los pocos restos camineros conocidos, se hace necesario emplear una nueva metodología de investigación: Se aborda el objeto como un estudio global, no sólo de los caminos, sino de todos los elementos interrelacionados con ellos, denominados como "espacios viales". Luego se presenta la indisoluble relación de los "espacios viales" con los castillos y torres ("espacios de control y defensa") en al-Andalus, como los vigilantes de los caminos, y se enuncia la toponimia árabe relacionada tanto con los "espacios viales" como con los "espacios de control y defensa". Finalmente, se recogen los datos que las diversas crónicas árabes nos proporcionan acerca de la política viaria en al-Andalus a lo largo del tiempo, así como sobre quién era el responsable de velar por el buen estado de los tramos viales.

Efficient Diastereo- and Enantioselective Synthesis of exo-Nitroprolinates by 1,3-Dipolar Cycloadditions Catalyzed by Chiral Phosphoramidite⋅Silver(I) Complexes

Chiral complexes formed by privileged phosphoramidites and silver triflate or silver benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between azomethine ylides generated from α-amino acid-derived imino esters and nitroalkenes affording with high dr the exo-cycloadducts 4,5-trans-2,5-cis-4-nitroprolinates in high ee at room temperature. In general, better results are obtained using silver rather than copper(II) complexes. In many cases the exo-cycloadducts can be obtained in enantiomerically pure form just after simple recrystallization. The mechanism and the justification of the experimentally observed stereodiscrimination of the process are supported by DFT calculations. These enantiomerically enriched exo-nitroprolinates can be used as reagents for the synthesis of nitropiperidines, by ester reduction and ring expansion, which are inhibitors of farnesyltransferase.

Synthesis of Chromen[4,3-b]pyrrolidines by Intramolecular 1,3-Dipolar Cycloadditions of Azomethine Ylides: An Experimental and Computational Assessment of the Origin of Stereocontrol

Azomethine ylides, generated from imine-derived O-cinnamyl or O-crotonyl salicylaldeyde and α-amino acids, undergo intramolecular 1,3-dipolar cycloaddition, leading to chromene[4,3-b]pyrrolidines. Two reaction conditions are used: (a) microwave-assisted heating (200 W, 185 °C) of a neat mixture of reagents, and (b) conventional heating (170 °C) in PEG-400 as solvent. In both cases, a mixture of two epimers at the α-position of the nitrogen atom in the pyrrolidine nucleus was formed through the less energetic endo-approach (B/C ring fusion). In many cases, the formation of the stereoisomer bearing a trans-arrangement into the B/C ring fusion was observed in high proportions. Comprehensive computational and kinetic simulation studies are detailed. An analysis of the stability of transient 1,3-dipoles, followed by an assessment of the intramolecular pathways and kinetics are also reported.