Ynone Promoted Deaminative Coupling of Gramines with - and -Nucleophiles.

The deaminative coupling of gramines with nucleophiles represents a versatile approach for structure diversification, but often involves non innocent conditions and/or reagents. Here a new acetylenic reagent is developed for the C-N bond activation of gramines and their in situ coupling with - and -centered nucleophiles. Using the new acid/base- and redox-neutral ynone reagent the coupling reactions proceed exceedingly as exemplified by the synthesis of several indol-3-ylmethyl derivatives, including new indole-benzodiazepine and indole-hydrazone conjugates.

Catalytic Asymmetric Synthesis of Bicyclic Isothioureas from a Common Enolizable Template.

While bicyclic isothiourea (ITU) moieties are found in biologically active molecules and organocatalysts, a catalytic asymmetric synthesis of ITUs is pending. Here, we report the catalytic, enantioselective functionalization of enolizable template with a variety of electrophiles, including unsaturated ketones, esters, sulfones, nitro compounds, and thiolating reagents, as an entry to enantioenriched bicyclic ITUs . Scope and limitations are shown, as well as examples of product derivatization.

Predictors of Hospitalization in Breakthrough COVID-19 among Fully Vaccinated Individuals with Immune-Mediated Rheumatic Diseases: Data from SAFER-Study.

Breakthrough COVID-19 (occurring in fully vaccinated people) has been described. Data on its characteristics among immune-mediated rheumatic disease (IMRD) patients are scarce. This study describes breakthrough COVID-19 occurring in IMRD patients participating in the SAFER-study, a Brazilian multicentric cohort evaluating the safety, effectiveness, and immunogenicity of SARS-CoV-2 vaccines in patients with autoimmune diseases.

Unsaturated chiral-only-at-metal rhodium(III) complexes bearing SiN-type ligands.

Enantiopure chiral-at-metal rhodium(III) unsaturated 16e complexes have been obtained from racemic [Rh(SiN)Cl] (SiN= 8-(dimethylsilyl)quinoline) using a readily accessible chiral spiroborate as chiral resolution agent. This strategy allows an easy access to enantiopure neutral Δ/Λ-Rh(SiN)2Cl and cationic Δ/Λ-Rh(SiN)2[BAr4F] unsaturated complexes, wherein rhodium(III) is coordinated to two inert silylquinoline ligands in a propeller-like arrangement.