Factores asociados a malestar psicológico durante la pandemia de COVID-19 en personal de salud de un hospital público de Ecuador / Related factors to psychological distress during the COVID-19 pandemic in the health staff of a public hospital in Ecuador

Fundamento: La pandemia por el coronavirus SARS-CoV-2, genera afectaciones en las esferas social, económica y sanitaria de un país, y de manera particular, consecuencias psicológicas negativas en el personal sanitario de hospitales públicos, considerados como la primera línea de atención a pacientes con esta enfermedad. Objetivo: Describir factores asociados a la presencia de malestar psicológico en el personal sanitario de un hospital general público en Ecuador, durante la pandemia de COVID-19. Metodología: Estudio no experimental, de corte transversal, con alcance descriptivo-correlacional. Los datos correspondieron a 276 funcionarios de la salud que respondieron un instrumento online, con un módulo de datos sociodemográficos y una escala de tamizaje de malestar psicológico, estos se aplicaron después de una intervención en salud dirigida al personal de salud realizada al inicio de la pandemia, en mayo del año 2020. Se realizaron análisis descriptivos y de asociación, mediante el software SPSS 25.0. Resultados: La muestra estuvo compuesta por 76.1 % de mujeres, 23.9 % de hombres, con una media de edad de 36 años, en mayor cantidad con profesionales de Enfermería (33.7 %), seguido de Medicina (24.3 %). El 70.7 % del personal de salud presentó malestar psicológico, de estos, el 26.1 % con indicativo de trastorno mental. Se encontraron tres variables asociadas a la presencia de malestar psicológico: clima laboral, teletrabajo y convivir con grupos de riesgo. Conclusiones: El personal de Salud ha presentado afectación en su salud mental asociado a las condiciones sociolaborales durante la pandemia.

Background: The SARS-CoV-2 coronavirus pandemic affects the social, economic and health spheres of a country, especially negative psychological consequences to the health staff of public hospitals, considered as the first line of care for patients with this disease. Objective: To describe factors related to the presence of psychological distress in the health personnel of a public general hospital in Ecuador, during the COVID-19 pandemic. Methodology: Non-experimental, cross-sectional study with a descriptive-correlational scope. The data corresponded to 276 health officials who answered to an online instrument, with a sociodemographic data module and a psychological distress screening scale, these were applied after a health intervention aimed at health personnel conducted at the beginning of the pandemic, in May 2020. Descriptive and association analyzes were performed using SPSS 25.0 software. Results: The sample was made up of 76.1 % women, 23.9 % men, mean age of 36 years, with a greater number of Nursing professionals (33.7 %), followed by Medicine (24.3 %). 70.7 % of the health personnel presented psychological distress, out of these, 26.1 % showed mental disorder. Three variables related to the presence of psychological distress were found: work environment, teleworking and living with risk groups. Conclusions: Health staff has presented mental health distress related to socio-labor conditions during the pandemic.

Acyl-Directed ortho-Borylation of Anilines and C7 Borylation of Indoles using just BBr3.

Indoles are privileged heterocycles found in many biologically active pharmaceuticals and natural products. However, the selective functionalization of the benzenoid moiety in indoles in preference to the more reactive pyrrolic unit is a significant challenge. Herein we report that N-acyl directing groups enable the C7-selective C-H borylation of indoles using just BBr3 . This transformation shows some functional-group tolerance and notably proceeds with C6 substituted indoles. The directing group can be readily removed in situ and the products isolated as the pinacol boronate esters. Acyl-directed electrophilic borylation can be extended to carbazoles and anilines with excellent ortho selectivity. 4-amino-indoles are amenable to this process, with acyl group installation and directed electrophilic C-H borylation enabling selective formation of C5-BPin-indoles.

Selective Boryl-Anion Migration in a Vinyl sp2 -sp3 Diborane Induced by Soft Borane Lewis Acids.

An intramolecular 1,2-boryl-anion migration from boron to carbon has been achieved by selective activation of the π system in [(vinyl)B2 Pin2 )]- using "soft" BR3 electrophiles (BR3 =BPh3 or 9-aryl-BBN). The soft character is key to ensure 1,2-migration proceeds instead of oxygen coordination/B-O activation. The BR3 -induced 1,2-boryl-anion migration represents a triple borylation of a vinyl Grignard reagent using only B2 Pin2 and BR3 and forms differentially protected 1,1,2-triborylated alkanes. Notably, by increasing the steric bulk at the ß position of the vinyl Grignard reagent used to activate B2 Pin2 , 1,2-boryl-anion migration can be suppressed in favor of intermolecular {BPin}- transfer to BPh3 , thus enabling simple access to unsymmetrical sp2 -sp3 diboranes.

Diboryldiborenes: π-Conjugated B4 Chains Isoelectronic to the Butadiene Dication.

B(sp2 )-B(sp3 ) diborane species based on bis(catecholato)diboron and N-heterocyclic carbenes (NHCs) underwent catechol/bromide exchange selectively at the sp3 -hybridized boron atom. The reduction of the resulting 1,1-dibromodiborane adducts led to reductive coupling and isolation of doubly NHC-stabilized 1,2-diboryldiborenes. These compounds are the first examples of molecules exhibiting π-electron delocalization over an all-boron chain.

Synthesis, Characterization, and Functionalization of 1-Boraphenalenes.

1-Boraphenalenes have been synthesized by reaction of BBr3 with 1-(aryl-ethynyl)naphthalenes, 1-ethynylnaphthalene, and 1-(pent-1-yn-1-yl)naphthalene and they can be selectively functionalized at boron or carbon to form bench-stable products. All of these 1-boraphenalenes have LUMOs localized on the planar C12 B core that are closely comparable in character to isoelectronic phenalenyl cations. In contrast to the comparable LUMOs, the aromatic stabilization of the C5 B ring in 1-boraphenalenes is dramatically lower than the C6 rings in phenalenyl cations. This is due to the occupied orbitals of π symmetry being less delocalised in the 1-boraphenalenes.

Catalytic Electrophilic C-H Borylation Using NHC⋠Boranes and Iodine Forms C2-, not C3-, Borylated Indoles.

Activation of N-heterocyclic carbene boranes (NHC⋅BH3 ) by I2 enables the metal-free catalytic C-H borylation of heteroarenes with formation of H2 as the by-product in a process that uses only bench stable precursors. The borylation of indoles using NHC⋅BH3 /I2 produces C2-borylated indoles exclusively in contrast to other catalytic electrophilic C-H borylation methods. Mechanistic studies indicate that this is due to C3 to C2 boron migration facilitated by the absence of exogenous Brønsted bases. Thus this C-H borylation methodology proceeds under sufficiently Brønsted acidic conditions to enable the thermodynamic C2-borylated indole isomer to be formed instead of the C3 borylated-isomer. This demonstrates that electrophilic C-H borylation can be used to access a wider range of borylated regioisomers than reported to date.

Quantitative Structure-Activity Relationships for the Nucleophilicity of Trivalent Boron Compounds.

We describe herein the development of quantitative structure-activity relationships (QSAR) for the nucleophilicity of trivalent boron compounds covering boryl fragments bonded to alkali and alkaline-earth metals, to transition metals, and to sp3 boron units in diboron reagents. We used the charge of the boryl fragment (q[B]) and the boron p/s population ratio (p/s) to describe the electronic structures of boryl moieties, whereas the distance-weighted volume (Vw ) descriptor was used to evaluate the steric effects. The three-term easy-to-interpret QSAR model showed statistical significance and predictive ability (r2 =0.88, q2 =0.83). The use of chemically meaningful descriptors has allowed identification of the factors governing the boron nucleophilicity and indicates that the most efficient nucleophiles are those with enhanced the polarization of the B-X bond towards the boron atom and reduced steric bulk. A detailed analysis of the potential energy surfaces of different types of boron substituents has provided insight into the mechanism and established an order of nucleophilicity for boron in B-X: X=Li>Cu>B(sp3 )>Pd. Finally, we used the QSAR model to make a priori predictions of experimentally untested compounds.

N-Heterocycle-Ligated Borocations as Highly Tunable Carbon Lewis Acids.

The relative (to BEt3) hydride ion affinity (HIA) of a series of acridine borenium salts has been calculated, with some HIAs found to be similar to that for [Ph3C]+. The HIA at the acridine C9 position is controlled by both acridine and the boron substituents, the latter presumably affecting the strength of the B=N bond in the acridane-BY2 products from hydride transfer. Through a range of hydride abstraction benchmarking reactions against organic hydride donors the experimental HIA of [F5acr-BCat]+ (cat = catechol, F5acr = 1,2,3,4,7-pentafluoroacridine) has been confirmed to be extremely high and closely comparable to that of [Ph3C]+. The high HIA of [F5acr-BCat]+ enables H2 and alkene activation in a FLP with 2,6-di-tert-butylpyridine. Finally, the HIA of pyridine and quinoline borenium cations has been determined, with the HIA at boron in [PinB(amine)]+ (pin = pinacol, amine = pyridine or quinoline) found to be relatively low. This enabled the hydroboration of pyridine and quinoline by HBPin to be achieved through the addition of 5-10 mol % of bench-stable cationic carbon Lewis acids such as 2-phenyl-N,N-dimethylimidazolium salts.

The carboboration of Me3Si-substituted alkynes and allenes with boranes and borocations.

The 1,1-carboboration of 1-Me3Si-1-alkynes is the dominant reaction observed using [PhBCl(2-DMAP)][AlCl4], 1, and PhBCl2 electrophiles, with highly substituted vinyl pinacol boronate esters isolated post esterification. Other aryl and heteroaryl congeners of both 1 and PhBCl2 have a limited scope in the 1,1-carboboration of 1-Me3Si-1-alkynes, with desilylboration more prevalent. PhBCl2 converts Me3Si-substituted allenes to allylboranes via a formal 1,3-carboboration with Me3Si-migration. [Cl2B(2-DMAP)][AlCl4] reacts with a number of 1-Me3Si-1-alkynes by desilylboration, whilst with Me3Si-ethyne a 1,1-boroamination reaction proceeds, which with excess boron electrophile is followed by an intermolecular desilylboration to form a tricationic-borate. The use of excess 1-Me3Si-1-propyne relative to 1 (and a thienyl congener of 1) formed 2-boradienes in low yields from the reaction with two equivalents of alkyne. Vinyl borocations ligated by 2,6-lutidine of the general formula, [(vinyl)BCl(2,6-lutidine)][AlCl4] formed 1-boradienes with 1-Me3Si-1-alkynes.

Correction: Unsymmetrical 1,1-diborated multisubstituted sp(3)-carbons formed via a metal-free concerted-asynchronous mechanism.

Correction for 'Unsymmetrical 1,1-diborated multisubstituted sp(3)-carbons formed via a metal-free concerted-asynchronous mechanism' by Ana B. Cuenca et al., Org. Biomol. Chem., 2015, 13, 9659-9664.

Unsymmetrical 1,1-diborated multisubstituted sp(3)-carbons formed via a metal-free concerted-asynchronous mechanism.

We have experimentally proved the unsymmetrical 1,1-diboration of diazo compounds, formed in situ from aldehydes and cyclic and non-cyclic ketones, in the absence of any transition metal complex. The heterolytic cleavage of the mixed diboron reagent, Bpin-Bdan, and the formation of two geminal C-Bpin and C-Bdan bonds has been rationalised based on DFT calculations to occur via a concerted-asynchronous mechanism. Diastereoselection is attained on substituted cyclohexanones and DFT studies provide understanding on the origin of the selectivity. The alkoxide-assisted selective deborylation of Bpin from multisubstituted sp(3)-carbon and generation of a Bdan stabilized carbanion, easily conducts a selective protodeboronation sequence.

Complete reductive cleavage of CO facilitated by highly electrophilic borocations.

The addition of CO to [((R3N)BH2)2(µ-H)][B(C6F5)4] leads to formation of trimethylboroxine ((MeBO)3) and [(R3N)2BH2][B(C6F5)4]. When R = Et, [(Et3N)H2B(µ-O)B(CH3)NEt3][B(C6F5)4], is isolated and demonstrated to be an intermediate in the formation of (MeBO)3.

Facile Arylation of Four-Coordinate Boron Halides by Borenium Cation Mediated Boro-desilylation and -destannylation.

The addition of AlCl3 to four-coordinate boranes of the general formula (C-N-chelate)BCl2 results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl]+. The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl3 were sufficient to effect high-yielding arylation of (C-N-chelate)BCl2. Boro-destannylation is more rapid than boro-desilylation and leads to double arylation at the boron center, whereas in reactions with arylsilanes either single or double arylation occurs dependent on the nucleophilicity of the arylsilane and on the electrophilicity of the borenium cation. The electrophilicity of the borenium cation derived from 2-phenylpyridine was greater than that of the benzothiadiazole analogues, enabling the boro-desilyation of less nucleophilic silanes and the direct electrophilic borylation of 2-methylthiophene.

Mixed diboration of alkenes in a metal-free context.

Experimental and theoretical rationalization on regioselective mixed diboration of alkenes, with the unsymmetrical diboron reagent Bpin-Bdan, providing the protecting Bdan moiety in the internal position.

Understanding α,ß-unsaturated imine formation from amine additions to α,ß-unsaturated aldehydes and ketones: an analytical and theoretical investigation.

A combination of in situ IR spectroscopy (ReactIR) and DFT calculations have been used to understand what factors govern the selectivity in the addition of primary amines to α,ß-unsaturated aldehydes and ketones, i.e., 1,2- versus 1,4-addition. It has been found that the 1,2-addition products (α,ß-unsaturated imines following addition and elimination) usually predominate for most systems. However, exceptions, such as methyl vinyl ketone, selectively give 1,4-addition products. This has been rationalized by DFT calculations that show that major conformational effects are involved, controlled mainly by steric effects of carbonyl substituents, resulting in a model that provides simple and predictable preparation of α,ß-unsaturated imines for in situ utilization in synthesis.

A clear-cut example of selective Bpin-Bdan activation and precise Bdan transfer on boron conjugate addition.

Activating the non-symmetrical Bpin-Bdan diboron reagent with alkoxide leads to the formation of two possible adducts: MeO(-) →Bpin-Bdan or MeO(-) →Bdan-Bpin. Experimental and theoretical investigation confirms that the MeO(-) →Bpin interaction is preferred and thus selective formation of a C-Bdan bond upon reaction with an activated C=C bond.

Disclosing the structure/activity correlation in trivalent boron-containing compounds: a tendency map.

Most trivalent boron reagents are electrophiles owing to the vacancy for two electrons to fill the outer orbital of boron; however, interestingly, trivalent boron compounds can change their electrophilic character to a nucleophilic character by only changing the nature of the substituents on the boron atoms. With the help of computational tools, we have analyzed the structural- and electronic properties of boryl fragments that were either bonded to main-group metals or coordinated to transition-metals/rare-earth-metals and we have designed a map that might help to identify certain trends. This trend map will be useful for selecting an appropriate trivalent boron compound, depending on the sought reactivity.

Trivalent boron nucleophile as a new tool in organic synthesis: reactivity and asymmetric induction.

Boron compounds have been traditionally regarded as "Lewis acids" preferring to accept electrons rather than donate them in the course of their reactions but current examples of unusual reactivity between tricoordinated boranes and electrophilic sites suggest a new conceptual context for the boryl moieties, based on their nucleophilic character which can be enhanced depending on the substituents on boron.

Catalytic non-conventional trans-hydroboration: a theoretical and experimental perspective.

We have studied the non-conventional trans-hydroboration reaction of alkynes both experimentally and theoretically. A catalytic system based on the in situ mixture of [{Rh(cod)Cl}(2)]/PCy(3) (cod=1,5-cyclooctadiene, Cy=cyclohexyl) has been able to activate pinacolborane and catecholborane and transfer boryl and hydride groups onto the same unhindered carbon atom of the terminal alkynes. The presence of a base (Et(3)N) favored the non-conventional trans-hydroboration over the traditional cis-hydroboration. Varying the substrate had a significant influence on the reaction, with up to 99% conversion and 94% regioselectivity observed for para-methyl-phenylacetylene. Both DFT and quantum mechanical/molecular mechanical ONIOM calculations were carried out on the [RhCl(PR(3))(2)] system. To explain the selectivity towards the (Z)-alkenylboronate we explored several alternative mechanisms to the traditional cis-hydroboration, using propyne as a model alkyne. The proposed mechanism can be divided into four stages: 1) isomerization of the alkyne into the vinylidene, 2) oxidative addition of the borane reagent, 3) vinylidene insertion into the Rh-H bond, and finally 4) reductive elimination of the C-B bond to yield the 1-alkenylboronate. Calculations indicated that the vinylidene insertion is the selectivity-determining step. This result was consistent with the observed Z selectivity when the sterically demanding phosphine groups, such as PCy(3) and PiPr(3), were introduced. Finally, we theoretically analyzed the effect of the substrate on the selectivity; we identified several factors that contribute to the preference for aryl alkynes over aliphatic alkynes for the Z isomer. The intrinsic electronic properties of aryl substituents favored the Z-pathway over the E-pathway, and the aryl groups containing electron donating substituents favored the occurrence of the vinylidene reaction channel.