Synthesis of IAN-type N,N-Ligands via Dynamic Kinetic Asymmetric Buchwald-Hartwig Amination

The Pd-catalyzed coupling of racemic heterobiaryl bromides, triflates, or nonaflates with aryl/alkyl primary amines using QUINAP as the ligand provides the corresponding axially chiral heterobiaryl amines with excellent yields and enantioselectivities. Reactivity and structural studies of neutral and cationic oxidative addition intermediates support a dynamic kinetic asymmetric amination mechanism based on the labilization of the stereogenic axis in the latter and suggest that coordination of the amine to the Pd center is the stereodetermining step.Ministerio de Ciencia e Innovación CTQ2013-48164-C2-1-P, CTQ2013-48164-C2-2-P, RYC-2013-12585 for A.R.European FEDER FundsJunta de Andalucía 2012/FQM 1078

Dynamic Kinetic Resolution of Hetero biaryl Ketones by Zinc- Catalyzed Asymmetr ic Hydrosil ylation

Adiastereo- and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile hetero- biaryl ketones is described. The DKR proceeds by zinc- catalyze dhydrosilylation of the carbonyl group ,thus leading to secondary alcohols bearing axial and central chirality .The strategy relies on the labilization of the stereogenic axis that takes place thanks to aLewis acid–base interaction between anitrogen atom in the heterocycle and the ketone carbonyl group .The synthetic utility of the methodology is demonstrated through stereospecific transformations into either N,N-ligands or appealing axially chiral, bifunctional thiourea organocata- lysts.Ministerio de Ciencia e Innovación (Grants CTQ2016-76908-C2-1-P, CTQ2016-76908-C2-2-P, contract RYC-2013-12585)European FEDER FundsJunta de Andalucía (Grant 2012/FQM 10787)European Union - Marie Skłodowska-Curie (COFUND—Grant Agreement n 8 8 291780

A Dynamic Kinetic Asymmetric Heck Reaction for the Simultaneous Generation of Central and Axial Chirality

A highly diastereo- and enantioselective, scalable Pd-catalyzed dynamic kinetic asymmetric Heck reaction of heterobiaryl sulfonates with electron-rich olefins is described. The coupling of 2,3-dihydrofuran or N-boc protected 2,3-dihydropyrrole with a variety of quinoline, quinazoline, phthalazine, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching excellent diastereo- and enantiomeric excesses when in situ formed [Pd0/DM-BINAP] was used as the catalyst, with loadings reduced down to 2 mol % in large scale reactions. The coupling of acyclic, electron-rich alkenes can also be performed using a [Pd0/Josiphos ligand] to obtain axially chiral heterobiaryl α-substituted alkenes in high yields and enantioselectivities. Products from Boc-protected 2,3-dihydropyrrole can be easily transformed into N,N ligands or appealing axially chiral, bifunctional proline-type organocatalysts. Computational studies suggest that a β-hydride elimination is the stereocontrolling step, in agreement with the observed stereochemical outcome of the reaction.Ministerio de Ciencia e Innovación (Grants CTQ2016-76908-C2-1-P; CTQ2016-76908-C2-2-P; CTQ2016-78083-P; RYC-2013-12585)European Commission (FEDER Programme)Junta de Andalucía (Grant 2012/FQM 10787)Universidad de Sevilla (Grant No. 1800511201)European Union - Marie Skłodowska-Curie (COFUND—Grant Agreement nº 291780

Relationships between depth and age, and recruitment indexes of hake on Galicia and Portugal shelf

In this paper it is studied the relations between the depth and the ages of the hake caugth in the six surveys done between 1974 and 1979 in the Divisions Vlllc and IXa, as soon as the recruitment levels in those years. It is observed a clear stratification of the ages and a significant bathimetric tendency to increase the mean age with the depth (1'=0.81). On the other hand, it is noticed a serious decrease in the following years over the recruitment level detected in 1974.Dans ce papier on a studie les relations entre l'âge et la profundeur du merlu capturée pendant six campagns realisées entre 1974 et 1979 dans subaire Vlllc et Division IXa du CIEM ainsi que les nivenux du recruitment durant ces annees. On observe une claire stratification entre la bathymetrie et l'âge et une tendence significatif a augmenter l'âge moyenne avec la profunder (r=0.81). D'antre coté, on constante une grave chute dans 1es anneés suivantes un relation avec le niveaux de recruitement detecté en 1974

Practical guide for pressure ulcers

La presente guía se integra dentro de la Colección de Guías Prácticas de Heridas del Servizo Galego de Saúde, de acuerdo con la estrategia y líneas de acción promovidas a través del Programa Ulceras Fuera que coordina la Subdirección Xeral de Ordenación Asistencial e Innovación Organizativa. Esta guía se conforma como una síntesis de las mejores intervenciones y prácticas preventivas o terapéuticas disponibles para el cuidado de las personas con úlceras pro presión o en riego de padecerlas.A presente guía intégrase dentro da Colección de Guías Prácticas de Feridas do Servizo Galego de Saúde; de acordo coas estratexias e liñas de acción promovida a través do Programa Úlceras Fóra que coordina a Subdirección Xeral de Ordenación Asistencial e Innovación Organizativa. Esta guía confórmase coma unha síntese das mellores intervencións e prácticas preventivas ou terapéuticas dispoñibles para o coidado das persoas con úlceras por presión ou con risco de padecelas

Use of sun gear orbits to obtain the load sharing in planetary transmissions and its impact in the tooth load

The present work assesses the possibility of using the orbits described by the sun gear in order to analyse the load sharing ratio in planetary gear transmissions. Furthermore, the current work is extended to observe the impact of the floatability and different tangential pinhole position errors in the load borne in a single contact between a pair of teeth in comparison to the load per planet. Therefore, it highlights the inaccuracy of the load sharing ratio (LSR) as an indicator of the overload in one tooth of the planet. Moreover, the use of the orbits represented with respect to a rotating reference provides helpful information to determine the overloads and underloads in the planets due to the existence of a tangential error in sequentially phased transmissions. Therefore, this proposal provides a simpler solution to the measurement of the LSR in planetary transmissions with different numbers of planets than the use of strain gauges.The authors would like to acknowledge Project DPI2017-85390-P funded by the Spanish Ministry of Economy, Industry, and Competitiveness for supporting this research. Moreover, the authors acknowledge the Project PID2020-116213RB-I00 funded by the Ministry of Science and Innovation

Interchangeability between the Data Obtained by Two Powermeters during Road Cycling Competitions: A Case Study

Various power meters are used to assess road-cycling performance in training and competition, but no previous study has analyzed their interchangeability in these conditions. Therefore, the purpose was to compare the data obtained from two different power meters (PowerTap vs. Power2Max) during cycling road races. A national-level under-23 male competitive cyclist completed six road-cycling official competitions (five road races and one individual time trial), in which power output was simultaneously registered with the two power meters. After this, the main power output variables were analyzed with the same software. The average and critical power obtained from the PowerTap power meter were slightly lower than from the Power2Max power meter (3.56 ± 0.68 and 3.62 ± 0.74 W·kg−1, 5.06 and 5.11 W·kg−1, respectively), and the correlations between both devices were very high (r ≥ 0.996 and p 7.50 W·kg−1 and power profile at 1, 5 and 10 s. In conclusion, the data obtained in competitions by the two power meters were interchangeable. Nevertheless, the Power2Max power meter underestimated the pedaling power during short and high-intensity intervals (≤10.0 s and >7.50 W·kg−1) compared to the PowerTap power meter. Therefore, the analysis of these efforts should be treated with caution.SIThis research received no external fundin

El proceso de catalogación de los fondos del Archivo Histórico de la Escuela Técnica Superior de Náutica y Máquinas Navales

En este trabajo se presenta el proceso de elaboración del inventario de los fondos del Archivo Histórico de la Escuela de Náutica (UPV/EHU). Además de tratarse del primer centro de nuestra universidad en iniciar un proceso de esta naturaleza, la disposición del inventario permitirá que los fondos puedan ser explotados y se podrá completar la historia de este centro docente.Nautikako Eskolako Artxibo Historikoaren (EHU) funtsen inbentarioa egiteko prozesua aurkezten da lan honetan. Gure unibertsitatean gisa horretako prozesua abiatzen duen lehen ikastegia izateaz gainera, inbentarioa erabiltzeko aukerak bide emango du horiek ustiatzeko eta, modu horretara, ikastegi horren historia osatu ahal izango da.Dans ce travail, on présente le processus d'élaboration de l'inventaire des fonds des Archives Historiques de l'École Nautique (UPV/EHU). Outre qu'il s'agit du premier centre de notre université à mettre en marche un processus de cette nature, la disposition de l'inventaire permettra que les fonds puissent être exploités et l'histoire de ce centre d'enseignement pourra être complétée.In this work, an introduction is made to the process of elaboration of the inventory of funds in the Historical Archives of the Superior Technical School of Navigation and Naval Machinery of the University of the Basque Country. Apart from being the first centre of our university in initiating a process of this nature, the layout of the inventory will allow for the exploitation of the funds and it will be then possible to complete the history of this teaching centre

Chirality and catalysis with aromatic N-fused heterobicyclic carbenes

The benzoannulation of the most common families of aromatic NHCs, imidazol-2-ylidenes and 1,2,4-triazol-3-ylidenes, results in heterobicyclic imidazo[1,5-a]pyridin-3-ylidenes (ImPy's) and [1,2,4]triazolo[4,3-a]pyridin-3-ylidenes (TriPy's), characterized by a bridged N atom. These are versatile platforms that offer multiple possibilities for the modulation of the steric and electronic properties of the carbene ligand and/or organocatalyst, and offer also diverse opportunities for the introduction of several types of chiralities. In this paper the different families of chiral ImPy and TriPy carbenes and their application in asymmetric catalysis will be discussed.España, Ministerio de Economía y Competitividad (CTQ2013-48164-C2-1-P, CTQ2013- 48164-C2-2-P, and predoctoral fellowship to C. I.),España Junta de Andalucía (Grant 2012/FQM 1078