Regio- and stereoselective oxyamination of dienes through a tandem rhodium-catalysed aziridination-nucleophilic opening affords racemic oxazolidinone derivatives, which undergo a kinetic resolution acylation process with amidine-based catalysts (ABCs) to achieve s values of up to 117. This protocol was applied to the enantioselective synthesis of sphingosine.

The introduction of fluoroalkylthioether groups has attracted the attention of the drug-discovery community given the special physicochemical and pharmacokinetic features they confer to bioactive compounds, yet these are often limited to standard SCF 3 and SCF 2 H moieties. Herein, two saccharin-based electrophilic reagents have been disclosed for the incorporation of uncommon SCF 2 CF 2 H and SCF 2 CF 3 motifs. Their reactivity performance, multigram-scale preparation, and divergent derivatization have been thoroughly investigated with a variety of nucleophiles, including natural products and pharmaceuticals.

The introduction of fluoroalkylthioether groups has attracted the attention of the drug discovery community given the special physicochemical and pharmacokinetic features they confer to bioactive compounds. Synthetic advances in the field have been capitalized by methods to incorporate SCF3 and SCF2H motifs, however, longer and synthetically more challenging polyfluoroethyl chains are still underdeveloped. Here, two saccharin-based electrophilic reagents have been disclosed for the efficient incorporation of SCF2CF2H and SCF2CF3 motifs. Their reactivity performance has been thoroughly investigated with a variety of nucleophiles such as thiols, alcohols, amines, alkenes, (hetero)aromatics, and organometallic species, including natural products and pharmaceuticals. Finally, multigram-scale preparation and divergent derivatization has been explored from SCF2CF2H derivatives.

SuFEx click chemistry has established itself as a formidable tool to rapidly and effectively link chemical structures. Despite tremendous advancements in the field in recent years, the installment of the crucial -SO2F handle still requires the use of purposely designed, expensive, and non-atom economical reagents. However, the use of the most obvious reagent, SO2F2, has been twarthed by the difficulties associated with the manipulation and dosage of this toxic gas, as well as its apparent low reactivity with amino functionalities. Herein, we disclose a modular flow platform, which is able to generate on demand, and safely dose, gaseous SO2F2. Due to the use of flow technology, many lingering limitations of this transformation could be overcome, resulting in significantly reduced reaction times, high reactivity and exceptional reaction scope. The effectiveness of the process was demonstrated by the successful synthesis of a diverse set of fluorosulfates and sulfamoyl fluorides, including those derived from biorelevant compounds, peptides, and proteins.

Matrix-assisted laser desorption ionization mass spectrometry imaging (MALDI-MSI) is a widely used technique for spatial metabolomics analysis, but the matrix introduces spectral interferences that impede data processing. In this study, we present an experimental and computational workflow utilizing isotopic labeling to discover and annotate matrix adducts in MALDI-MSI. Our approach enables the removal of matrix-related signals, improving metabolite annotation accuracy, extending metabolome coverage, and facilitating the interpretation of tissue morphology.