Magma storage and migration associated with the 2011–2012 El Hierro eruption: Implications for crustal magmatic systems at oceanic island volcanoes
 Starting in July 2011, anomalous seismicity was observed at El Hierro Island, a young oceanic island volcano. On 12 October 2011, the process led to the beginning of a submarine NW‐SE fissural eruption at ~15 km from the initial earthquake loci, indicative of significant lateral magma migration. Here we conduct a multifrequency, multisensor interferometric analysis of spaceborne radar images acquired using three different satellite systems (RADARSAT‐2, ENVISAT, and COSMO‐SkyMed (Constellation of Small Satellites for Mediterranean Basin Observation)). The data fully captures both the pre‐eruptive and coeruptive phases. Elastic modeling of the ground deformation is employed to constrain the dynamics associated with the magmatic activity. This study represents the first geodetically constrained active magmatic plumbing system model for any of the Canary Islands volcanoes, and one of the few examples of submarine volcanic activity to date. Geodetic results reveal two spatially distinct shallow (crustal) magma reservoirs, a deeper central source (9.5 ± 4.0 km), and a shallower magma reservoir at the flank of the southern rift (4.5 ± 2.0 km). The deeper source was recharged, explaining the relatively long basaltic eruption, contributing to the observed island‐wide uplift processes, and validating proposed active magma underplating. The shallowest source may be an incipient reservoir that facilitates fractional crystallization as observed at other Canary Islands. Data from this eruption supports a relationship between the depth of the shallow crustal magmatic systems and the long‐term magma supply rate and oceanic lithospheric age. Such a relationship implies that a factor controlling the existence/depth of shallow (crustal) magmatic systems in oceanic island volcanoes is the lithosphere thermomechanical behavior.
González, Pablo J.; Samsonov, Sergey V.; Pepe, Susi; Tiampo, Kristy F.; Tizzani, Pietro; Casu, Francesco; Fernández, José; Camacho, Antonio G.; Sansosti, Eugenio
Sequential Norrish type II photoelimination and intramolecular aldol cyclization of α-diketones: Synthesis of polyhydroxylated cyclopentitols by ring contraction of hexopyranose carbohydrate derivatives
The excitation of the innermost carbonyl of nono‐2,3‐diulose derivatives by irradiation with visible‐light initiates a sequential Norrish type II photoelimination and aldol cyclization process that finally gives polyfunctionalized cyclopentitols. The rearrangement has been confirmed by the isolation of stable acyclic photoenol intermediates that can be independently cyclized by a thermal 5‐(enolexo)‐exo‐trig uncatalyzed aldol reaction with high diastereoselectivity. In this last step, the large deuterium kinetic isotope effect found for the 1,5‐hydrogen atom transfer seems to indicate that the aldol reaction runs through a concerted pericyclic mechanism. Owing to the ready availability of pyranose sugars of various configurations, this protocol has been used to study the influence of pyranose ring‐substituents on the diastereoselectivity of the aldol cyclization reaction. In contrast with other pyranose ring contraction methodologies no transition‐metal reagents are needed and the sequential rearrangement occurs simply by using visible light and moderate heating (0 to 60 °C).
Álvarez‐Dorta, Dimitri; León, Elisa I.; Kennedy, Alan R.; Martín, Ángeles; Pérez-Martín, Inés; Riesco-Fagundo, Concepción; Suárez, Ernesto
Connecting Discrete Stereoclusters by Using DFT and NMR Spectroscopy: The Case of Nivariol
he structural determination of small organic molecules is mainly undertaken by using NMR techniques, although it is increasingly supplemented by using computational methods. NMR parameters, such as chemical shifts and coupling constants, are extremely sensitive indicators of local molecular conformation and are a source of structural evidence. However, their interpretation is fairly challenging in many circumstances, such as the case of the new polyether squalene derivative nivariol, the structure of which was elucidated by means of NMR spectroscopy and DFT calculations. The potential flexibility of this molecule and the high number of quaternary carbon atoms that it contains make its configurational assignment very difficult. Moreover, the relative configuration of four separated stereoclusters was established and subsequently connected by using NOE and J‐based analysis, as well as by a comparison of its experimental 13C NMR chemical shifts with the corresponding population‐weighted values, as calculated by using DFT methods. Limitations of these used approaches became apparent but were overcome by combining the two methods.
Cen‐Pacheco, Francisco; Rodríguez, Jaime; Norte, Manuel; Fernández, José J.; Hernández Daranas, Antonio
Multicomponent Ligation of Steroids: Creating Diversity at the Linkage Moiety of Bis-spirostanic Conjugates by Ugi Reactions
The diversity-oriented synthesis of novel bis-spirostanic conjugates utilizing two different Ugi four-component reactions (Ugi-4CR) is described. Spirostanic steroids were functionalized with Ugi-reactive groups, that is, amines, isocyanides, and carboxylic acids, and next were subjected to multicomponent ligation approaches leading to bis-steroidal conjugates featuring pseudo-peptidic and heterocyclic linkage moieties. Both the classic Ugi-4CR and its hydrazoic acid variant were implemented, proving good efficiency for the ligation of isocyanosteroids to spirostanic acids and equatorial amines. Axially oriented amines showed poorer results, although model studies proved that chemical efficiency could be significantly improved while increasing reaction times. Overall, the method comprises the rapid generation of molecular diversity at the bis-steroid linkage moiety and, consequently, shows promise toward the production of combinatorial libraries of bis-spirostanes for biological screening.
Pérez-Labrada, Karell; Méndez, Yanira; Brouard, Ignacio; Rivera, Daniel G.
A Novel Approach for the Evaluation of Positive Cooperative Guest Binding: Kinetic Consequences of Structural Tightening
Cooperativity is one of the most relevant features displayed by biomolecules. Thus, one of the challenges in the field of supramolecular chemistry is to understand the mechanisms underlying cooperative binding effects. Traditionally, cooperativity has been related to multivalent receptors, but Williams et al. have proposed a different interpretation based on the strengthening of noncovalent interactions within receptors upon binding. According to such an interpretation, positive cooperative binding operates through structural tightening. Hence, a quite counterintuitive kinetic behavior for positively cooperative bound complexes may be postulated: the more stable the complex, the slower it is formed. Such a hypothesis was tested in a synthetic system in which positive cooperative binding was previously confirmed by calorimetric experiments. Indeed, a linear correlation between the thermodynamics (ΔG°) and the kinetics (ΔG≠) of guest binding confirmed the expected behavior. These distinctive kinetics provide solid evidence of positive cooperative guest binding, which is particularly useful bearing in mind that kinetic experiments are frequently and accurately carried out in both synthetic and biological systems.
Carrillo Fumero, Romen; Morales, E. ; Martín, Víctor S.; Martín, Tomás
Epoxide-opening cascades triggered by a Nicholas reaction: Total synthesis of teurilene
Natural inspiration: Based on the biosynthesis of squalene‐derived polyethers, a total synthesis of teurilene is described. The carbocation formation in the Nicholas reaction serves to control the initiation of a polyepoxide ring‐opening cascade. The three furan rings present in teurilene were obtained in excellent yield in one step. Boc=tert‐butoxycarbonyl, TMS=trimethylsilyl.
Rodríguez-López, Julio; Pinacho Crisóstomo, Fernando R.; Ortega, Nuria; López Rodríguez, Matías; Martín, Víctor S.; Martín, Tomás
Synthesis of Chiral β-Iodo- and Vinylorganophosphorus(V) Compounds by Fragmentation of Carbohydrate Anomeric Alkoxyl Radicals
A new general methodology for the synthesis of chiral vinylphosphonate and vinylphosphine oxide carbohydrate derivatives has been developed using the anomeric alkoxyl radical fragmentation reaction as the key step. The synthetic sequence proceeded via β-iodophosphonate and β-iodophosphine oxide intermediates, which may be interesting synthons for the introduction of phosphorus into organic molecules. These vinylphosphonates could be easily transformed into 2-methylene-1-phosphapentofuranoses (3-methylene-1,2-oxaphospholanes) and β-aminophosphonates, isosteres of biologically active α-methylene-γ-lactones and β-amino acids, respectively.
Hernández-Guerra, Daniel; Rodríguez Morales, María S.; Suárez, Ernesto
Iron(III) Catalyzed Direct Synthesis of cis-2,7-Disubstituted Oxepanes. The Shortest Total Synthesis of (+)-Isolaurepan
Prins cyclization of bis-homoallylic alcohols with aldehydes catalyzed by iron(III) salts shows excellent cis selectivity and yields to form 2,7-disubstituted oxepanes. The iron(III) is able to catalyze this process with unactivated olefins. This cyclization was used as the key step in the shortest total synthesis of (+)-isolaurepan.
Purino, Martín A.; Ramírez, Miguel A.; Daranas, Antonio: Martín, Víctor; Padrón, Juan I.
Conformation and Chiral Effects in α,β,α-Tripeptides
Short α,β,α-tripeptides comprising a central chiral trisubstituted β2,2,3*-amino acid residue form unusual γ-turns and δ-turns in CDCl3 and DMSO-d6 solutions but do not form β-turns. Thermal coefficients of backbone amide protons, 2D-NMR spectra, and molecular modeling revealed that these motifs were strongly dependent on the configuration (chiral effect) of the central β-amino acid residue within the triad. Accordingly, SSS tripeptides adopted an intraresidual γ-turn like (C6) arrangement in the central β-amino acid, whereas SRS diastereomers preferred an extended δ-turn (C9) conformation. A different SRS-stabilizing bias was observed in the crystal structures of the same compounds, which shared the extended δ-turn (C9) found in solution, but incorporated an additional extended β-turn (C11) to form an overlapped double turn motif.
Saavedra, Carlos J.; Boto, Alicia; Hernández, Rosendo; Miranda, José Ignacio; Aizpurua, Jesus M.
Synthesis of α,γ-peptide hybrids by selective conversion of glutamic acid units
The site-selective modification of small peptides at a glutamate residue allows the ready preparation of α,γ-hybrids. In this way, a single peptide can be transformed into a variety of hybrid derivatives. The process takes place under very mild conditions, and good global yields are obtained.
Saavedra, Carlos J.; Boto, Alicia; Hernández, Rosendo