Estudio observacional de los intentos autolíticos en el ámbito de emergencias

El intento de suicidio es considerado un importante problema de salud pública y mental con gran impacto en la sociedad, de tal índole que aproximadamente por cada segundo se produce un intento autolítico a nivel mundial. Debido a estas cifras tan sorprendentes se decidió iniciar un programa de recogida de datos por parte del equipo de emergencias de Valladolid sobre los casos de intentos de suicidio atendidos para desarrollar un perfil de conducta autolítica mediante la información relevante obtenida tras su análisis. Este proyecto se llevó a cabo mediante un estudio observacional prospectivo de un muestra constituida por 76 pacientes atendidos por la Unidad Medicalizada de Emergencias de Valladolid 1 por padecimiento de tentativa suicida y/o presencia de ideación suicida en el año 2015-2016, con vista a evaluar su perfil. El intento de suicidio predominó en el sexo femenino y en el rango de edad de 50-59 años, siendo el método autolítico de elección la intoxicación medicamentosa. Destacó significativamente la presencia de ideación suicida, depresión y tratamiento psiquiátrico habitual en estos pacientes, así como el consumo de alcohol antes del acto suicida. Tras la obtención de estos datos se observó que la restricción a medios autolíticos, control farmacológica y revisión médica periódica podrían ser alternativas efectivas para la reducción del gran número de intentos de suicido.Grado en Enfermerí

A general protocol to afford enantioenriched linear homoprenylic amines

The reaction of a readily obtained chiral branched homoprenylamonium salt with a range of aldehydes, including aliphatic substrates, affords the corresponding linear isomers in good yields and enantioselectivities.We thank the Spanish Ministerio de Ciencia e Innovación for their financial support (CTQ2011-24165). I. B. acknowledges the Generalitat Valenciana for a predoctoral fellowship (ACIF/2011/159)

Regio- and Stereoselective Aminopentadienylation of Carbonyl Compounds

A simple and robust protocol is detailed for the preparation of enantioenriched α-substituted (1,4-pentadien-3-yl)amine derivatives. The methodology involves the addition of an in situ formed pentadienyl indium reagent to chiral tert-butylsulfinimines, previously formed in the same pot. The addition takes place with excellent γ-regio- and diastereoselectivity for a wide range of carbonyl compounds, including α-unsubstituted aldehydes and methyl alkyl ketones. The catalytic hydrogenation of the sulfinamines obtained provides a convenient access to chiral α-substituted (3-pentyl)amines. The hydroboration–oxidation of the α-(1,4-pentadien-3-yl)amine derivatives, followed by a cyclization under Mitsunobu conditions, takes place with an excellent diastereoselectivity governed by the chiral sulfinyl group.We thank the Spanish Ministerio de Ciencia e Innovación (CTQ2011-24165) for financial support. I.B. acknowledges the Generalitat Valenciana for a predoctoral fellowship (ACIF/2011/159). E.B. acknowledges the Council of Higher Education- Turkey for a postdoctoral fellowship (16.10.12-B.09.6.YÖK.0.71.01-207.02-12285)

Oxidative Coupling of 4-Hydroxycoumarins with Quinoxalin-2(1H)-ones Induced by Visible Light under Aerobic Conditions

Direct and selective C(sp2)-H/C(sp2)-H cross-dehydrogenative coupling has become a promising strategy to increase molecular complexity with a high atom economy. This study describes an efficient and straightforward protocol for the regioselective C3-H/C3-H cross-coupling of 4-hydroxycoumarin derivatives with quinoxalin-2(1H)-ones, including late-stage modification of natural drugs, promoted by visible light under aerobic conditions at room temperature. With this approach, a wide range of hybrid drug-like molecules were prepared, using air as the terminal oxidant. Remarkably, the C4 OH group at the coumarin ring is essential for the reaction and has been used as a handle for diverse functionalizations of the final products. Moreover, sunlight can promote the reaction under very mild and sustainable conditions, even on a gram scale. Qualitative and semi-quantitative tools were used to demonstrate the greenness advance of this methodology over previously reported ones. Several experiments were conducted to propose a plausible mechanism for this transformation.This work was financially supported by the Spanish Ministerio de Ciencia e Innovación (grant no. CTQ2017-88171-P), Generalitat Valenciana (SEJIGENT/2021/005, granted to I. B.), and the University of Alicante (GRE20-03-A granted to I. B.)

Natural Tetraponerines: A General Synthesis and Antiproliferative Activity

A stereocontrolled general methodology to access all natural tetraponerines from (+)-T1 to (+)-T8 is detailed. Two consecutive indium-mediated aminoallylations with the appropriate enantiomer of chiral N-tert-butylsulfinamide and a thermodynamic control at the aminal stereocenter allow the formation of each natural tetraponerine with excellent stereoselectivity. The use of 4-bromobutanal in the first aminoallylation leads to the formation of 5–6–5 tetraponerines, while 5-bromopentanal is required to build the scaffold of 6–6–5 tetraponerines. A cross-metathesis reaction of the second aminoallylation product with cis-3-hexene is used to elongate the side chain up to 5 carbons so as to prepare the tetraponerines T5 to T8. The anticancer activity of these heavier tetraponerines against four different carcinoma human cell lines is examined, observing a promising cytotoxic activity of (+)-T7 against breast carcinoma cell line MCF-7.We thank the Spanish Ministerio de Ciencia e Innovación for their financial support (CTQ2011-24165). I.B. acknowledges the Generalitat Valenciana for a predoctoral fellowship (ACIF/2011/159)

Electrochemically site-selective alkoxylation of twisted 2-arylbenzoic acids via spirolactonization

The Electrochemical Cross-Dehydrogenative Coupling (ECDC) of twisted biphenyl-2-carboxylic acids with aliphatic alcohols provides 4′-alkoxyspirolactones which isomerize, under mild basic conditions, to give 4′-alkoxy-2-phenylbenzoic acids. This site-selective alkoxylation was readily adapted to 1 mmol scale and is environmentally friendly, as no terminal oxidants are needed and H2 is the only residue. The suitability of diphenic acid derivatives in this two-step protocol is noteworthy, especially for axially chiral substrates that can be functionalized with retention of the configuration and of the enantiomeric purity. We have proposed a plausible mechanism based on experimental pieces of evidence that support the single-electron oxidation of the carboxylate, formed by deprotonation of the biphenyl-2-carboxylic acids with 2,6-lutidine, and DFT calculations that suggest a very fast spirocyclization of the intermediate σ-aroyloxyl radical. Competing pathways to benzocoumarins were also examined by computational studies.This work was generously supported by the Spanish Ministerio de Ciencia, Innovación y Universidades (MICIU; grant no. CTQ2017-88171-P) and the University of Alicante (grant no. VIGROB-285/19). I. B. acknowledges the Spanish MICIU for a Juan de la Cierva-incorporación grant (no. IJCI-2017-33706)

Alkanes in Minisci-Type Reaction under Photocatalytic Conditions with Hydrogen Evolution

We report herein a protocol for the selective activation of C(sp3)–H bonds based on the interplay of two readily available organic catalysts and their successful implementation in cross-coupling azaarenes with alkanes. This Minisci-like reaction is promoted by visible light at room temperature and is free from chemical oxidants, metals, and chlorinated solvents. A wide range of substrates are compatible, including some bioactive molecules. Mechanistic studies support a dual catalytic cycle with H2 evolution.This work was financially supported by the Generalitat Valenciana (SEJIGENT/2021/005 and IDIFEDER/2021/13) and the University of Alicante (GRE20-03-A granted to I. B.)

Synthesis of Propargylamines by Cross-Dehydrogenative Coupling

Propargylamines are versatile compounds for heterocyclic synthesis, some of which are current drugs prescribed to treat patients with Parkinson’s disease. There are different methods to synthesize propargylamines, however, modern chemistry has moved progressively to rely on new strategies that meet the principles of Green Chemistry. In this context, propargylamines are readily accessible by the cross-dehydrogenative coupling (CDC) of two C-H bonds (i.e., NCsp3-H and Csp-H bonds); surely, CDC can be considered the most atom-economic and efficient manner to form C-C bonds. The aim of this review is to provide a comprehensive survey on the synthesis of propargylamines by the CDC of amines and terminal alkynes from three fronts: (a) transition-metal homogeneous catalysis, (b) transition-metal heterogeneous catalysis and (c) photoredox catalysis. A section dealing with the asymmetric synthesis of chiral propargylamines is also included. Special attention is also devoted to the proposed reaction mechanisms.This work was generously supported by the Spanish Ministerio de Ciencia, Innovación y Universidades (MICIU; grant no. CTQ2017-88171-P), the Generalitat Valenciana (GV; grant no. AICO/2017/007) and the Instituto de Síntesis Orgánica (ISO). I.B. is also grateful to the Spanish MICIU for a Juan de la Cierva-incorporación grant (no. IJCI-2017-33706)