Efforts to develop alternatives to triflic anhydride (Tf2O) as a trifluoromethylation reagent continue due to its limitations, including volatility, corrosiveness, and moisture sensitivity. Described herein is the use of a trifluoromethylsulfonylpyridinium salt (TFSP), easily obtained by a one-step reaction of Tf2O with 4-dimethylaminopyridine, as a reagent for the trifluoromethylative difunctionalization of alkenes by photoredox catalysis. DMSO and CH3CN are suitable solvents for achieving keto- and amino-trifluoromethylation of alkenes, respectively, with good functional group tolerance.

Rationale Recently N-Fluoroarenesulfonamides (ArSO2NHF) were found to be promising precursors for the preparation of N-fluorobenzenesulfonimide derivatives without applying F2. However, very few studies have discussed the mass spectrometric behaviors of ArSO2NHF with N-F structure. Methods In this article, we applied high-resolution electrospray ionization tandem mass spectrometry (HR-ESI-MS/MS) to study the effect on the mass spectrometric behaviors of ArSO2NHF after the introduction of the F-atom to the N-atom of ArSO(2)NH2. Results High-resolution electrospray ionization mass spectrometry (HR-ESI-MS) experiments showed that ArSO2NHF produced only good signals in negative ion mode, and the dominating product ion SO2F- at m/z 83 was observed in all HR-ESI-MS/MS of ArSO2NF- with different substituents in the Ar group. The formation of the product ion SO2F- was proof of the gas-phase F-atom migration rearrangement from the N-atom to the S-atom in ESI-MS/MS of ArSO2NF-. Conclusion To fully explain the gas-phase reaction mechanism from ArSO2NF- to SO2F-, we studied the HR-ESI-MS/MS of deprotonated ArSO2NHF and also performed theoretical calculations. Both results confirmed that ArSO2NF- first underwent Smiles rearrangement to yield intermediate I (INT1) ArNFSO2-, and then the F-atom of ArNFSO2- migrated from the N-atom to the S-atom to form intermediate II (INT2) ArN-SO2F, which finally dissociated to SO2F- at m/z 83 with loss of a neutral nitrene (ArN). All these results showed that the formation of the product ion SO2F- from ArSO2NF- was a common and intrinsic gas-phase reactivity of ArSO2NF-.

This study delves into the ion recognition capabilities of a novel host molecule, emphasizing the role of conformational locking in dictating ion selectivity. By employing the Buchwald-Hartwig cross-coupling reaction, we have notably shifted the ion receptor's selectivity from K+ to Na+. The findings are supported by computational simulations that reveal differences in binding energies and molecular strain impacting ion recognition. This innovative structural modification broadens the scope for alterations at the calix[4]arene's lower rim, paving the way for new methods and strategies in modulating ion recognition selectivity.

C-Oligosaccharides are metabolically stable surrogates of native glycans containing O/N/S-glycosidic linkages and thus have therapeutic potential. Here we report a straightforward approach to the synthesis of vinyl C-linked oligosaccharides via the Ni-catalyzed reductive hydroglycosylation of alkynyl glycosides with glycosyl bromides.

A wide range of Cu(II)-catalyzed C-H activation reactions have been realized since 2006, however, whether a C-H metalation mechanism similar to Pd(II)-catalyzed C-H activation reaction is operating remains an open question. To address this question and ultimately develop ligand accelerated Cu(II)-catalyzed C-H activation reactions, realizing the enantioselective version and investigating the mechanism is critically important. With a modified chiral BINOL ligand, we report the first example of Cu-mediated enantioselective C-H activation reaction for the construction of planar chiral ferrocenes with high yields and stereoinduction. The key to the success of this reaction is the discovery of a ligand acceleration effect with the BINOL-based diol ligand in the directed Cu-catalyzed C-H alkynylation of ferrocene derivatives bearing an oxazoline-aniline directing group. This transformation is compatible with terminal aryl and alkyl alkynes, which are incompatible with Pd-catalyzed C-H activation reactions. This finding provides an invaluable mechanistic information in determining whether Cu(II) cleaves C-H bonds via CMD pathway in analogous manner to Pd(II) catalysts. Ligands capable of accelerating and inducing enantioselectivity in C-H activations with base metal catalysts have remained elusive. Here, the authors report a ligand-accelerated enantioselective C-H alknylation, using a chiral BINOL ligand with a copper catalyst.

Prof. Xiyan Lu will always be remembered for his development of organic reactions under phosphine or palladium catalysis, especially for phosphine-catalyzed [3 + 2] cycloadditions of electron-deficient allenes or alkynes with electrophiles such as electron-deficient alkenes and imines, known as Lu's [3 + 2] reaction. In addition to contributing to science, Prof. Lu left his mark as an educator by training the next generations of chemists and passing his work ethic on to his collaborators.

Rett syndrome (RTT) is a devastating neurodevelopmental disorder primarily caused by mutations in the methyl-CpG binding protein 2 (Mecp2) gene. Here, we found that inhibition of Receptor- Interacting Serine/Threonine- Protein Kinase 1 (RIPK1) kinase ameliorated progression of motor dysfunction after onset and prolonged the survival of Mecp2-null mice. Microglia were activated early in myeloid Mecp2- deficient mice, which was inhibited upon inactivation of RIPK1 kinase. RIPK1 inhibition in Mecp2- deficient microglia reduced oxidative stress, cytokines production and induction of SLC7A11, SLC38A1, and GLS, which mediate the release of glutamate. Mecp2- deficient microglia release high levels of glutamate to impair glutamate- mediated excitatory neurotransmission and promote increased levels of GluA1 and GluA2/3 proteins in vivo, which was reduced upon RIPK1 inhibition. Thus, activation of RIPK1 kinase in Mecp2- deficient microglia may be involved both in the onset and progression of RTT.