A General Platform for Visible Light Sulfonylation Reactions Enabled by Catalytic Triarylamine EDA Complexes.

Catalytic electron donor-acceptor (EDA) complexes have recently emerged as a powerful and sustainable alternative to iridium- and ruthenium-based photoredox synthetic methods. Yet, these complexes remain underexplored and reliant on the use of meticulously designed acceptors that require previous installation. Herein, we report a novel EDA complex employing tris(4-methoxyphenyl) amine as a catalytic donor for the sulfonylation of alkenes using inexpensive and readily available sulfonyl chlorides. Applying this operationally simple, visible-light-mediated general platform, we report both the redox-neutral and net-reductive functionalization of more than 60 substrates, encompassing vinylic or allylic sulfonylation, hydrosulfonylation, and sulfamoylation of activated and unactivated alkenes and alkynes.

Green chemistry meets medicinal chemistry: a perspective on modern metal-free late-stage functionalization reactions.

The progress of drug discovery and development is paced by milestones reached in organic synthesis. In the last decade, the advent of late-stage functionalization (LSF) reactions has represented a valuable breakthrough. Recent literature has defined these reactions as the chemoselective modification of complex molecules by means of C-H functionalization or the manipulation of endogenous functional groups. Traditionally, these diversifications have been accomplished by organometallic means. However, the presence of metals carries disadvantages related to their cost, environmental hazard and health risks. Fundamentally, green chemistry directives can help minimize such hazards through the development of metal-free LSF methodologies. In this review, we expand the current discussion on metal-free LSF reactions by providing an overview of C(sp2)-H, and C(sp3)-H functionalizations, as well as the utilization of heteroatom-containing functional groups as chemical handles. Selected topics such as metal-free cross-dehydrogenative coupling (CDC) reactions, organocatalysis, electrochemistry and photochemistry are also discussed. By writing the first review on metal-free LSF methodologies, we aim to highlight current advances in the field with examples that reveal specific challenges and solutions, as well as future research opportunities.

Synthesis of α-(perfluoroalkylsulfonyl)propiophenones: a new set of reagents for the light-mediated perfluoroalkylation of aromatics.

In response to the demand for late-stage perfluoroalkylation in synthetic chemistry, we report the synthesis of a series of bench-stable α-(perfluoroalkylsulfonyl)propiophenones. Their application as photocleavable reagents was tested with electron-rich aromatics under metal-free, redox- and pH-neutral conditions to enable late-stage perfluorooctylation, perfluorohexylation, and perfluorobutylation.

Synthesis of 2,5-Diaryl Nonsymmetric Furans C6-Platform Chemicals via Catalytic Conversion of Biomass and the Formal Synthesis of Dantrolene.

Biomass-derived commodity chemical 5-hydroxymethyl furfural is an underutilized C6-platform chemical derived from cellulose that is ideal to prepare next-generation value-added products. We have developed an efficient synthetic strategy to access 2,5-diaryl nonsymmetric furans from 5-hydroxymethyl furfural utilizing decarboxylative cross-couplings. A key finding was that the presence of the hydroxymethyl handle enhances the yields of the palladium-catalyzed decarboxylative cross-coupling reaction. The method provides access to a broad-range nonsymmetric 2,5-diaryl furans where each arene can be systematically introduced as required. Additionally, this green synthetic strategy was employed for a formal synthesis of the muscle relaxant Dantrolene in excellent yields.

Modern methods for the synthesis of perfluoroalkylated aromatics.

Perfluoroalkyl-containing substances (PFAS), have become omnipresent materials in the modern world for both commercial and research applications. Compounds such as perfluoroalkylated arenes and heteroarenes have found uses in surfactants, lubricants, and flame retardants as a result of their astonishing chemical stability. Consequently, the synthesis of such compounds encompasses a large body of scientific articles and patents developed in the previous century. Most recent reviews on this subject have thus focused on summarizing this traditional literature, and have thereby spurred the development of a new wave of reaction manifolds employing modern synthesis principles. This new generation of methodologies focuses on the greener synthesis of perfluoroalkylated aromatic scaffolds, through the use of more efficient organometallic reactions, as well as by photochemical and electrochemical strategies. Herein, we will summarize this cohort of reactions while highlighting current challenges and future desirable outcomes for their environmentally friendly synthesis.

EDA mediated S-N bond coupling of nitroarenes and sodium sulfinate salts.

Despite their long-known photochemical properties and their industrial value, the use of nitroarenes as a productive photochemical handle in organic synthesis has remained relatively unexplored. More specifically, the photochemical formation of nitrogen-sulfur bonds from nitroarenes remains to be demonstrated. Herein, we report the design and application of a sulfinate-nitroarene electron donor-acceptor (EDA) complex and its subsequent use in the first light mediated catalyst-free synthesis of N-hydroxy-sulfonamides. The presence of the EDA was assessed spectroscopically and studied via DFT and TD-DFT calculations. A total of 32 examples including both electron withdrawing and electron donating groups were synthesized under our oxygen- and water-tolerant conditions.

Triarylamines as catalytic donors in light-mediated electron donor-acceptor complexes.

Recently, photochemistry of Electron Donor-Acceptor (EDA) complexes employing catalytic amounts of electron donors have become of interest as a new methodology in the catalysis field, allowing for decoupling of the electron transfer (ET) from the bond-forming event. However, examples of practical EDA systems in the catalytic regime remain scarce, and their mechanism is not yet well-understood. Herein, we report the discovery of an EDA complex between triarylamines and α-perfluorosulfonylpropiophenone reagents, catalyzing C-H perfluoroalkylation of arenes and heteroarenes under visible light irradiation in pH- and redox-neutral conditions. We elucidate the mechanism of this reaction using a detailed photophysical characterization of the EDA complex, the resulting triarylamine radical cation, and its turnover event.

Franz Diffusion Cell Approach for Pre-Formulation Characterisation of Ketoprofen Semi-Solid Dosage Forms.

This study aimed to evaluate and compare, using the methodology of Franz diffusion cells, the ketoprofen (KTP) releasing profiles of two formulations: A gel and a conventional suspension. The second aim was to show that this methodology might be easily applied for the development of semi-solid prototypes and claim proof in pre-formulation stages. Drug release analysis was carried out under physiological conditions (pH: 5.6 to 7.4; ionic strength 0.15 M; at 37 °C) for 24 h. Three independent vertical Franz cells were used with a nominal volume of the acceptor compartment of 125 mL and a diffusion area of 2.5 cm². Additionally, two different membranes were evaluated: A generic type (regenerated cellulose) and a transdermal simulation type (Strat-M®). The KTP permeation profiles demonstrated that depending on the membrane type and the vehicle used, the permeation is strongly affected. High permeation efficiencies were obtained for the gel formulation, and the opposite effect was observed for the suspension formulation. Moreover, the permeation studies using Strat-M membranes represent a reproducible methodology, which is easy to implement for pre-formulation stage or performance evaluation of semi-solid pharmaceutical products for topical or transdermal administration.

Flujogramas quirúrgicos en el trauma protocolizado por algoritmos / Flujogramas surgical in the trauma protocolizado by algorithms

Los servicios hospitalarios de emergencia y en los servicios quirúrgicos y de auxiliares de diagnóstico ha recopilado una serie de indicaciones para la atención de los politraumatizados, prácticamente en todas las especialidades quirúrgicas, Urgencias, Neurocirugía, Cirugía Cardiotorácica, Cirugía General, Urología, Otorrinolaringología, Oftalmología, Gineco-obstetricia, Cirugía Vascular, Traumatología, Anestesia, Terapia Intensiva, Cirugía Plástica, Enfermería, Imagenología y Laboratorio en los diferentes capítulos de este flujograma..

Stress / Stress

Expone las principales relaciones del estres con patologías de otras especialides medicas como ginecología, oftalmología, nutrición, psicología, entre otras. Presenta el tratamiento general y la farmacología recomendada para el efecto...

Flujogramas en el truma protocolizado por algoritmos / Flujogramas in the trauma protocolizado by algorithms

Presenta un análisis descriptivo del progreso alcanzado en las ciencias quirúrgicas y la atención de traumas severos gracias a innovaciones tecnológicas, como programas de computadora o flujogramas para el diagnóstico y tratamiento de enfermedades. El estudio se basa en la aplicación de algoritmos, es decir, plantea los procedimientos correctos como conjuntos ordenados y finitos de operaciones en búsqueda de la solución...