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)

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)

Submillimetre compactness as a critical dimension to understand the main sequence of star-forming galaxies

We study the interstellar medium (ISM) properties as a function of the molecular gas size for 77 infrared-selected galaxies at z ∼ 1.3, having stellar masses 109.4 ≲ M⋆ ≲ 1012.0 M⊙ and star formation rates 12 ≲ SFRFIR ≲ 1000 M⊙ yr−1. Molecular gas sizes are measured on ALMA images that combine CO(2-1), CO(5-4), and underlying continuum observations, and include CO(4-3), CO(7-6) + [CI](3P2 − 3P1), [CI](3P1 − 3P0) observations for a subset of the sample. The ≳46 per cent of our galaxies have a compact molecular gas reservoir, and lie below the optical discs mass–size relation. Compact galaxies on and above the main sequence have higher CO excitation and star formation efficiency than galaxies with extended molecular gas reservoirs, as traced by CO(5-4)/CO(2-1) and CO(2-1)/LIR, SF ratios. Average CO + [CI] spectral line energy distributions indicate higher excitation in compacts relative to extended sources. Using CO(2-1) and dust masses as molecular gas mass tracers, and conversion factors tailored to their ISM conditions, we measure lower gas fractions in compact main-sequence galaxies compared to extended sources. We suggest that the submillimetre compactness, defined as the ratio between the molecular gas and the stellar size, is an unavoidable information to be used with the main sequence offset to describe the ISM properties of galaxies, at least above M⋆ ≥ 1010.6 M⊙, where our observations fully probe the main sequence scatter. Our results are consistent with mergers driving the gas in the nuclear regions, enhancing the CO excitation and star formation efficiency. Compact main-sequence galaxies are consistent with being an early post-starburst population following a merger-driven starburst episode, stressing the important role of mergers in the evolution of massive galaxies

The IR Compactness of Dusty Galaxies Set Star-formation and Dust Properties at z~0-2

Surface densities of gas, dust and stars provide a window into the physics of star-formation that, until the advent of high-resolution far-infrared/sub-millimeter observations, has been historically difficult to assess amongst dusty galaxies. To study the link between infrared (IR) surface densities and dust properties, we leverage the Atacama Large Millimetre/Submillimetre Array (ALMA) archive to measure the extent of cold dust emission in 15 $z\sim2$ IR selected galaxies selected on the basis of having available mid-IR spectroscopy from Spitzer. We use the mid-IR spectra to constrain the relative balance between dust heating from star-formation and active galactic nuclei (AGN), and to measure emission from Polycylic Aromatic Hydrocarbons (PAHs) -- small dust grains that play a key role in the photoelectric heating of gas. In general, we find that dust-obscured star-formation at high IR surface densities exhibits similar properties at low- and high-redshift, namely: local luminous IR galaxies have comparable PAH luminosity to total dust mass ratios as high-$z$ galaxies, and star-formation at $z\sim0-2$ is more efficient at high IR surface densities despite the fact that our sample of high$-z$ galaxies are closer to the main-sequence than local luminous IR galaxies. High star-formation efficiencies are coincident with a decline in the PAH/IR luminosity ratio reminiscent of the deficit observed in far-infrared fine-structure lines. Changes in the gas and dust conditions arising from high star-formation surface densities might help drive the star-formation efficiency up. This could help explain high efficiencies needed to reconcile star-formation and gas volume densities in dusty galaxies at cosmic noon.Comment: 18 pages, 10 figures, accepted to Ap

Evaluación continua y análisis de resultados en las asignaturas del grado de química impartidas por el departamento de química orgánica

En esta comunicación se pondrán en común las experiencias de distintos docentes del Departamento que han impartido asignaturas de Química Orgánica tanto en la antigua Licenciatura como en el nuevo Grado de Químicas. Las asignaturas en que se focaliza el estudio, debido a que son de obligada realización, son: Química Orgánica, Estereoquímica Orgánica, Determinación Estructural de Compuestos Orgánicos y Química Orgánica Avanzada. El objetivo de este estudio permitirá evaluar los cambios que se han llevado a cabo desde el punto de vista de las nuevas metodologías docentes que se han debido aplicar así como de los cambios de contenido que han sufrido las asignaturas. También se pretende evaluar los resultados obtenidos por los alumnos resaltando y comparando las ventajas e inconvenientes encontradas en el nuevo plan de estudios. Además, como fin último este estudio pretende poner en común aquellas estrategias que mejor resultado hayan dado desde distintos ámbitos docentes para aplicarlas en futuros cursos

Diverging results of areal and volumetric bone mineral density in Down syndrome

Population with Down syndrome (DS) has lower areal BMD, in association with their smaller skeletal size. However, volumetric BMD and other indices of bone microarchitecture, such as trabecular bone score (TBS) and calcaneal ultrasound (QUS), were normal. INTRODUCTION: Patients with DS have a number of risk factors that could predispose them to osteoporosis. Several studies reported that people with DS also have lower areal bone mineral density, but differences in the skeletal size could bias the analysis. METHODS: Seventy-five patients with DS and 76 controls without intellectual disability were recruited. Controls were matched for age and sex. Bone mineral density (BMD) was measure by Dual-energy X-ray Absorptiometry (DXA), and volumetric bone mineral density (vBMD) was calculated by published formulas. Body composition was also measured by DXA. Microarchitecture was measured by TBS and QUS. Serum 25-hidroxyvitamin D (25OHD), parathyroid hormone (PTH), aminoterminal propeptide of type collagen (P1NP), and C-terminal telopeptide of type I collagen (CTX) were also determined. Physical activity was assessed by the International Physical Activity Questionnaires (IPAQ-short form). To evaluate nutritional intake, we recorded three consecutive days of food. RESULTS: DS individuals had lower height (151 ± 11 vs. 169 ± 9 cm). BMD was higher in the controls (lumbar spine (LS) 0.903 ± 0.124 g/cm2 in patients and 0.997 ± 0.115 g/cm2 in the controls; femoral neck (FN) 0.761 ± .126 g/cm2 and 0.838 ± 0.115 g/cm2, respectively). vBMD was similar in the DS group (LS 0.244 ± 0.124 g/cm3; FN 0.325 ± .0.073 g/cm3) and the controls (LS 0.255 ± 0.033 g/cm3; FN 0.309 ± 0.043 g/cm3). Microarchitecture measured by QUS was slightly better in DS, and TBS measures were similar in both groups. 25OHD, PTH, and CTX were similar in both groups. P1NP was higher in the DS group. Time spent on exercise was similar in both groups, but intensity was higher in the control group. Population with DS has correct nutrition. CONCLUSIONS: Areal BMD is reduced in DS, but it seems to be related to the smaller body and skeletal size. In fact, the estimated volumetric BMD is similar in patients with DS and in control individuals. Furthermore, people with DS have normal bone microarchitecture

Dust and gas in star forming galaxies at z~3 - extending galaxy uniformity to 11.5 billion years

We present millimetre dust emission measurements of two Lyman Break Galaxies at z~3 and construct for the first time fully sampled infrared spectral energy distributions (SEDs), from mid-IR to the Rayleigh-Jeans tail, of individually detected, unlensed, UV-selected, main sequence (MS) galaxies at z=3. The SED modelling of the two sources confirms previous findings, based on stacked ensembles, of an increasing mean radiation field with redshift, consistent with a rapidly decreasing gas metallicity in z > 2 galaxies. Complementing our study with CO[3-2] emission line observations, we measure the molecular gas mass (M_H2) reservoir of the systems using three independent approaches: 1) CO line observations, 2) the dust to gas mass ratio vs metallicity relation and 3) a single band, dust emission flux on the Rayleigh-Jeans side of the SED. All techniques return consistent M_H2 estimates within a factor of ~2 or less, yielding gas depletion time-scales (tau_dep ~ 0.35 Gyrs) and gas-to-stellar mass ratios (M_H2/M* ~ 0.5-1) for our z~3 massive MS galaxies. The overall properties of our galaxies are consistent with trends and relations established at lower redshifts, extending the apparent uniformity of star-forming galaxies over the last 11.5 billion years

Rate and duration of hospitalisation for acute pulmonary embolism in the real-world clinical practice of different countries : Analysis from the RIETE registry

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