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Synthesis 11.22

Synthesis of five-membered organoborate heterocycles via a metal-free carboboration and their use in cross-coupling reactions

Isabel Valencia, David Sucunza, Patricia García-García, Adrián Pérez-Redondo, Juan Vaquero López

Synthesis 2022, Accepted Articles
DOI: 10.1055/a-1979-6009

Treatment of various vinylbenzopyridines with allyl(dichloro)borane affords five-membered organoborate heterocycles via a metal-free carboboration. The reaction between these organoborates and Grignard reagents increases the number of derivatives belonging to this novel family of four-coordinate organoboron compounds. Some of them were used as reagents in phenylations and methylations in moderate to high yields under standard palladium-catalyzed cross-coupling reaction conditions.

Milián et al. Advanced Synthesis & Catalysis. 2022;n/a(n/a):. Synthesis of Phenanthrene-Based Polycycles by Gold(I)-Catalyzed Cyclization of Biphenyl-Embedded Trienynes.

Publications > Milián et al

Synthesis of Phenanthrene-Based Polycycles by Gold(I)-Catalyzed Cyclization of Biphenyl-Embedded Trienynes.

Resumen

No hay resumen

Virumbrales et al. Organic Letters. 2022;:. Gold(I) Catalysis Applied to the Stereoselective Synthesis of Indeno[2,1-b]thiochromene Derivatives and Seleno Analogues.

Publications > Virumbrales et al

Gold(I) Catalysis Applied to the Stereoselective Synthesis of Indeno[2,1-b]thiochromene Derivatives and Seleno Analogues.

Resumen

No hay resumen

Adv. Synth. Catal. 10.22

Synthesis of Phenanthrene-based Polycycles by Gold(I)-Catalyzed Cyclization of Biphenyl-Embedded Trienynes

Ana Milián, Patricia García-García,* Juan J. Vaquero, Roberto Sanz, Manuel Ángel Fernández-Rodríguez*

Adv. Synth. Catal. 2022, Accepted Articles
DOI: 10.1002/adsc.202200887

Gold(I)-catalyzed cyclization of o-alkenyl-o’-alkynylbiaryls in the presence of external or internal nucleophiles provides a straightforward access to phenanthrene-based polycycles, which are of considerable interest in materials science. Thus, their reactions with alcohols yield functionalized dihydrophenanthrenes, in a process that can also be carried out intramolecularly to provide phenanthrene-derived heteropolycyclic compounds. Moreover, benzo[b]triphenylenes can be synthesized from o-methoxyvinyl-o’-alkynylbiaryls, in a reaction in which an (hetero)aryl substituent at the triple bond acts as an internal nucleophile.

Front. Pharmacol. 08.22

Steviol glycosides as an alternative osmotic agent for peritoneal dialysis fluid

Kopytina Valeria, Pascual-Antón Lucía, Toggweiler Nora, Arriero-País Eva-María, Strahl Lisa, Albar-Vizcaíno Patricia, Sucunza David, Vaquero Juan J., Steppan Sonja, Piecha Dorothea, López-Cabrera Manuel, González-Mateo Guadalupe-Tirma

Front. Pharmacol. 2022
DOI: 10.3389/fphar.2022.868374

Sánchez-Pavón et al. Journal. 2022;205:110323. Highly efficient unbridged D-A+(D) chromophores based on the quinolizinium cation for nonlinear optical (NLO) applications.

Publications > Sánchez-Pavón et al

Highly efficient unbridged D-A+(D) chromophores based on the quinolizinium cation for nonlinear optical (NLO) applications.

Resumen

Novel charged D-A+ chromophores based on quinolizinium cations as acceptor unit have been prepared by treating haloquinolizinium salts with N-heteroarylstannanes under Stille reaction conditions. This approach provides an easy access to potential one-dimensional D-A+ and two-dimensional D-A+-D chromophores in which the acceptor moiety (A+) is the simple azonia cation and the donors are different π-rich N-heterocycles. The first hyperpolarizabilities (β) were measured by hyper-Rayleigh scattering experiments and the experimental data confirmed that the inherent polarization between donor and acceptor fragments modulates the NLO properties. The electronic structures and properties (including both the linear and nonlinear optical properties) of the quinolizinium chromophores were examined by theoretical (DFT, HF and MP2) calculations. A promising strategy for the rational design of D-A building blocks to create new organic-based NLO materials is proposed.

Sans-Panadés et al. Org Lett. 2022;24(31):5860-5865. Synthesis of BN-Polyarenes by a Mild Borylative Cyclization Cascade.

Publications > Sans-Panadés et al

Synthesis of BN-Polyarenes by a Mild Borylative Cyclization Cascade.

Universidad de Alcalá (IRYCIS). Departamento de Química Orgánica y Química Inorgánica, Instituto de Investigación Química "Andrés M. del Río" (IQAR). Campus Científico-Tecnológico, Facultad de Farmacia. Autovía A-II, Km 33.1, 28805-Alcalá de Henares, Madrid, Spain.

Abstract

Reaction of BCl(3) with suitably substituted o-alkynylanilines promotes a cascade reaction in which BN-polycyclic compounds are obtained via the formation of two new cycles and three new bonds in a single operational step. The reaction is highly efficient and takes place at room temperature, providing a very mild and straightforward strategy for the preparation of BN-aromatic compounds, which can be further transformed into a variety of BN-PAHs with different polycyclic cores and substituents.

Kopytina et al. Front Pharmacol. 2022;13:868374. Steviol glycosides as an alternative osmotic agent for peritoneal dialysis fluid.

Publications > Kopytina et al

Steviol glycosides as an alternative osmotic agent for peritoneal dialysis fluid.

1. Department of Immunology, Molecular Biology Research Center Severo Ochoa (CBMSO), Spanish National Research Council (CSIC), Madrid, Spain.  2. Fresenius Medical Care Deutschland GmbH, Frankfurter, St. Wendel, Germany.  3. Department of Nephrology, IdiPAZ Research Institute, La Paz University Hospital, Madrid, Spain.  4. Department of Organic and Inorganic Chemistry, Faculty of Pharmacy, University of Alcalá (IRYCIS), Madrid, Spain.  5. Fresenius Medical Care Deutschland GmbH, St. Wendel, Germany.

Abstract

Background: Peritoneal dialysis (PD) is a renal replacement technique that requires repeated exposure of the peritoneum to hyperosmolar PD fluids (PDFs). Unfortunately, it promotes alterations of the peritoneal membrane (PM) that affects its functionality, including mesothelial-mesenchymal transition (MMT) of mesothelial cells (MCs), inflammation, angiogenesis, and fibrosis. Glucose is the most used osmotic agent, but it is known to be at least partially responsible, together with its degradation products (GDP), for those changes. Therefore, there is a need for more biocompatible osmotic agents to better maintain the PM. Herein we evaluated the biocompatibility of Steviol glycosides (SG)-based fluids. Methods: The ultrafiltration and transport capacities of SG-containing and glucose-based fluids were analyzed using artificial membranes and an in vivo mouse model, respectively. To investigate the biocompatibility of the fluids, Met-5A and human omental peritoneal MCs (HOMCs) were exposed in vitro to different types of glucose-based PDFs (conventional 4.25% glucose solution with high-GDP level and biocompatible 2.3% glucose solution with low-GDP level), SG-based fluids or treated with TGF-β1. Mice submitted to surgery of intraperitoneal catheter insertion were treated for 40 days with SG- or glucose-based fluids. Peritoneal tissues were collected to determine thickness, MMT, angiogenesis, as well as peritoneal washings to analyze inflammation. Results: Dialysis membrane experiments demonstrated that SG-based fluids at 1.5%, 1%, and 0.75% had a similar trend in weight gain, based on curve slope, as glucose-based fluids. Analyzing transport capacity in vivo, 1% and 0.75% SG-based fluid-exposed nephrectomized mice extracted a similar amount of urea as the glucose 2.3% group. In vitro, PDF with high-glucose (4.25%) and high-GDP content induced mesenchymal markers and angiogenic factors (Snail1, Fibronectin, VEGF-A, FGF-2) and downregulates the epithelial marker E-Cadherin. In contrast, exposition to low-glucose-based fluids with low-GDP content or SG-based fluids showed higher viability and had less MMT. In vivo, SG-based fluids preserved MC monolayer, induced less PM thickness, angiogenesis, leukocyte infiltration, inflammatory cytokines release, and MMT compared with glucose-based fluids. Conclusion: SG showed better biocompatibility as an osmotic agent than glucose in vitro and in vivo, therefore, it could alternatively substitute glucose in PDF.

Altarejos et al. European Journal of Organic Chemistry. 2022;2022(30):e202200521. Synthesis of Tri- and Tetrasubstituted Alkenyl Boronates from Alkynes.

Publications > Altarejos et al

Synthesis of Tri- and Tetrasubstituted Alkenyl Boronates from Alkynes.

Resumen

The synthesis of organoboron compounds have attracted the attention of the synthetic community. In particular, molecules with C(sp2)-B bonds enable the transformation to new C?C or C-heteroatom bonds by well-established methodologies. Alkenyl boronates have the possibility for further conversion of the boron moiety or functionalization of the double bond. This review gives an overview on the recent methodologies for the selective preparation of the challenging highly substituted alkenyl boronates from alkynes.

Dyes and Pigments 08.22

Highly efficient unbridged D-A+(D) chromophores based on the quinolizinium cation for nonlinear optical (NLO) applications

Esmeralda Sánchez-Pavón, Javier Recio, Marco Antonio Ramirez, Belen Batanero, Koen Clays, Francisco Mendicuti, Gema Marcelo, Thais Carmona, Obis Castaño, Silvia Angelova, Jose L. Andres, Juan J. Vaquero, Ana M. Cuadro*

Dyes and Pigments 2022, ASAP
DOI: 10.1016/j.dyepig.2022.110323

Novel charged D-A+ chromophores based on quinolizinium cations as acceptor unit have been prepared by treating haloquinolizinium salts with N-heteroarylstannanes under Stille reaction conditions. This approach provides an easy access to potential one-dimensional D-A+ and two-dimensional D-A+-D chromophores in which the acceptor moiety (A+) is the simple azonia cation and the donors are different π-rich N-heterocycles. The first hyperpolarizabilities (β) were measured by hyper-Rayleigh scattering experiments and the experimental data confirmed that the inherent polarization between donor and acceptor fragments modulates the NLO properties. The electronic structures and properties (including both the linear and nonlinear optical properties) of the quinolizinium chromophores were examined by theoretical (DFT, HF and MP2) calculations. A promising strategy for the rational design of D-A building blocks to create new organic-based NLO materials is proposed.