Coupled domino processes: Synthesis of 3,5,8-trisubstituted coumarins from propargyl vinyl ethers

The generation of a small and representative library of 3,5,8-trisubstituted coumarins (21 compounds, 7 families, 3 groups) is described. The library was built from the corresponding propargyl vinyl ethers and three different 1,3-dicarbonyl derivatives using a one-pot coupled domino strategy. These coumarins constitute a novel chemotype defined by the presence of a chemical handle in the pyranone ring and a varied substitution pattern adorning the aromatic ring, which includes fluorine- or oxygen-containing functionalities. © 2013 American Chemical Society.This research was supported by the Spanish Ministerio de Economía y Competitividad (MICINN) and the European Regional Development Fund (CTQ2011- 28417-C02-02). L.C. thanks the Spanish MEC for an FPI grant.Peer Reviewe

Synthesis of Fully Substituted Pyrimidines

A novel approach to the synthesis of fully substituted pyrimidine derivatives armed with an oxy-functionalized acetate chain at the ring is described. The manifold uses amidines as the nitrogen source and activated skipped diynes as the electrophilic reactive partners in a coupled domino strategy. In the first domino reaction, two consecutive aza-Michael additions assemble the six-membered ring heterocycle, while in the second domino process, a [H]-shift and a [3,3]-sigmatropic rearrangement lead to the aromatization of the product.This research was supported by the Spanish Ministerio de Economía y Competitividad (MICINN) and the European Regional Development Fund (CTQ2011- 28417-C02-02). S.L.T. thanks the Spanish MEC for an FPU grant.Peer Reviewe

A convenient domino access to substituted alkyl 1,2-dihydropyridine- 3carboxylates from propargyl enol ethers and primary amines

A convenient domino access to substituted alkyl 1,2-dihydropyridine-3- carboxylates from propargyl enol ethers and primary amines was reported. A solution of propargyl sinyl ether 1a and p-anisidine in toluene was placed in a microwave-special closed vial and the solution was irradiated for 30 minutes in a single-mode microwave oven. The reaction mixture was dried over anhydrous sodium sulfate and filtrated using dichloromethane as solvent. After removing the solvent at reduced pressure the products were purified by flash column chromatography. Accordingly, the microwave irradiation of an ethanolic mixture of propargyl enol ether 1 a and MeONH2.HCl in the presence of NaOAc yielded the methyl 2-phenyl-4-pyridinecarboxylate in a convenient 54% yield. These results seem to point out to a new reaction pathway involving different thermally-driven rearrangements of the 2,4-dienal 3 intermediate.This research was supported by the Spanish Ministerio de Ciencia e Innovación, the European Regional Development Fund (CTQ2005-09074-C02-02 and CTQ2008-06806-C02-02) and the Spanish MSC ISCIII (RETICS, RD06/0020/1046, and RD06/0020/0041), CSIC (Proyecto Intramural Especial 200719), FUNCIS (REDESFAC PI01/06 and 35/06) and the Fundación Instituto Canario de Investigación del Cancer (FICI-G.I.N808/2007). G.M.-A. thanks Spanish MEC for a FPU grant.Peer Reviewe

Web de apoyo a una aplicación Android de fisioterapia

Las aplicaciones de apoyo a la salud se están convirtiendo en herramientas necesarias en el día a día, tanto las destinadas a los profesionales sanitarios como las dirigidas solamente a los pacientes. Sin embargo, no todas las áreas de la medicina están suficientemente apoyadas por este tipo de aplicaciones. En concreto, la fisioterapia es uno de las áreas de la salud que necesita un mayor esfuerzo en este sentido. En este Trabajo Fin de Grado se propone el desarrollo de una Web que sirva de apoyo a la aplicación Android que ha sido desarrollada en conjunto con Jairo Méndez y Javier Mallo, gracias a ella se podrán realizar tareas de forma sencilla que con la aplicación resultarían complicadas y poco útiles. Con la versión Web se podrán realizar las mismas tareas que se realizaban con la aplicación Android (obtener información sobre las clínicas asociadas a la aplicación, realizar reservas, interactuar con su fisioterapeuta asignado pudiendo contactar con él y recibir consejos y ejercicios adecuados para su problema), a mayores de estas funcionalidades se podrán realizar otras, como bloquear unas determinadas horas de la clínica, para que no se puedan realizar reservas durante ese periodo, administrar y gestionar todos los productos y servicios ofrecidos (modificar, añadir o borrar los tratamientos o ejercicios), que la aplicación móvil no poseía, y que son necesarias para el efectivo funcionamiento del servicio.Grado en Ingeniería de Tecnologías Específicas de Telecomunicació

General synthesis of substituted 1,2-dihydropyridines

A general and practical metal-free protocol for the synthesis of 1,2-dihydropyridines with wide structural/functional diversity at the ring and featuring mono, double, or spiro substitution at the sp3 position is described. The protocol entails a microwave-assisted domino reaction of a propargyl vinyl ether (secondary or tertiary) and a primary amine (aliphatic or aromatic) in toluene or methanol. © 2014 American Chemical Society.This research was supported by the Spanish Ministerio de Economı́a y Competitividad (MICINN) and the European Regional Development Fund (CTQ2011-28417-C02-02). L.C. and G.M.-A. thank the Spanish MEC for FPI and FPU grants, respectively.Peer Reviewe

Merging domino and redox chemistry: Stereoselective access to di- and trisubstituted β,γ-unsaturated acids and esters

Merging is the game! The coupling of a domino reaction and an internal neutral redox reaction constitutes an excellent manifold for the stereoselective synthesis of di- and trisubstituted olefins featuring a malonate unit, an ester, or a free carboxylic acid as substituents at the allylic position (see scheme; MW=microwave). The reaction utilizes simple starting materials (propargyl vinyl ethers), methanol or water as solvents, and a very simple and bench-friendly protocol. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.This research was supported by the Spanish MICINN and the European RDF (CTQ2008–06806-C02–02), the Spanish MSC ISCIII (RETICS RD06/0020/1046), FUNCIS (REDESFAC PI01/06). G. M.-A. and L. C. thank Spanish MEC for FPU and FPI grants, respectively.Peer Reviewe

Non-destructive techniques (NDT) for the diagnosis of heritage buildings: Traditional procedures and futures perspectives

It is estimated that EU cultural heritage (CH) buildings represent 30% of the total existing stock. Nevertheless, all actions in terms of refurbishment need a deep knowledge based on the diagnosis of the built quality. For this reason, the paper aims to provide a comprehensive review about the applicability of non-destructive techniques (NDT) and advanced modelling technologies for the diagnosis of heritage buildings. Considering a time span of two decades (2001–2021), a bibliometric analysis was performed, using data statistics and science mapping. Subsequently, the most relevant studies on this topic were evaluated for each technique. The main findings revealed that: (i) most of studies were conducted on Southern European countries; (ii) 36% of publications were journal papers and only 2% corresponded to reviews; (iii) “photogrammetry” and “laser applications” were identified as consolidated techniques for historic preservation, but they are only linked with HBIM and deep learning; (iv) a significant gap on quantitative NDT was detected and consequently, future researches should be performed to propose a common diagnosis protocol; (v) artificial neural networks have several barriers (i.e. data privacy, network security and quality of datasets). Hence, a holistic approach should be adopted by the European countries

The free-linking task: a graph-inspired method for generating non-disjoint similarity data with food products

"Free sorting", in which subjects are asked to sort a set of items into groups of "most similar" items, is increasingly popular as a technique for profiling sets of foods. However, free sorting implies an unrealistic model of sample similarity: that similarity is purely binary (is/is not similar) and that similarity is fully transitive (similarities {A, B} and {B, C} imply {A, C}). This paper proposes a new method of rapid similarity testing -- the "free-linking" task -- that solves both problems: in free linking, subjects draw a similarity graph in which they connect pairs of samples with a line if they are similar, according to the subject s individual criteria. This simple task provides a more realistic model of similarity which allows degrees of similarity through the graph distance metric and does not require transitive similarity. In two pilot studies with spice blends (10 samples, 58 subjects) and chocolate bars (10 samples, 63 subjects), free linking and free sorting are evaluated and compared using DISTATIS, RVb, and the graph parameters degree, transitivity, and connectivity; subjects also indicated their preferences and ease-of-use for the tasks. In both studies, the first two dimensions of the DISTATIS consensus were highly comparable across tasks; however, free linking provided more discrimination in dimensions three and four. RVb stability was equivalent for the two methods. Graph statistics indicated that free linking had greater discrimination power: on average subjects made similarity groupings with lower degree, lower transitivity, and higher connectivity for free linking in both studies. However, subjects did overall find free sorting easier and liked it more, indicating a higher cognitive difficulty of free linking. The free-linking task, therefore, provides more robust, realistic similarity maps at the cost of higher panelist effort, and should prove a valuable alternative for rapid sensory assessment of product sets.Agencia Estatal de Investigació

Tertiary skipped diynes: A pluripotent building block for the modular and diversity-oriented synthesis of nitrogen heterocycles

Dominos! The multivalent reactivity profile of tertiary skipped diynes has been conveniently exploited in the domino and diversity-oriented synthesis of fully substituted pyrazoles and 1, 4-diazepane derivatives (see scheme). The developed manifold is chemically efficient and simple to operate. In addition, the resulting Ncontaining heterocycles are obtained in a regio- and chemoselective manner. (Chemical Equation Presented) © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.This research was supported by the Spanish Ministerio de Ciencia e Innovación, the European Regional Development Fund (CTQ2008-06806-C02-02), the Spanish MSC ISCIII (RETICS RD06/0020/1046), FUNCIS (REDESFAC PI01/06) and the Fundación Instituto Canario de Investigación del Cancer (FICI-G.I.N808/2007). S.L.-T. thanks the Spanish MEC for an FPU grant. The authors thank technician Anna Jurado Varona for her experimental assistance.Peer Reviewe