A new method of constructing ArSCF2CF2Cu from ArSCu and TMSCF2Br (TMS=trimethylsilyl) has been developed. The cross-coupling reactions of the obtained ArSCF2CF2Cu with diverse aryl iodides (Ar ' I) provide an efficient access to Ar ' CF2CF2SAr. Mechanistic studies demonstrate that the ArSCF2CF2Cu species were generated through controllable double difluoromethylene insertions into ArS-Cu bonds rather than the 1,2-addition of ArSCu to tetrafluoroethylene.

Narrowband organic afterglow materials show application in multiplexed bioimaging and others. However, materials featuring an intrinsic narrowband afterglow with an emission lifetime >100 ms remain elusive. We report a serendipitous finding of a chemical reaction from aromatic amine to luminescent acridone. Interestingly, upon doping into a suitable matrix, luminescent acridone molecules display a narrowband deep-blue afterglow with full widths at half-maximum 40 nm and CIEy 0.08 under ambient conditions. The narrowband emission originates from the multiresonant thermally activated delayed fluorescence (MRTADF) due to the suppressed vibronic coupling and rigid molecular backbone in the acridone system. Compared to conventional ones, here the MRTADF emitters feature modest k(RISC) of 1-10 s(-1) and ultralong delayed fluorescence lifetime >100 ms, which are further fashioned into an aqueous system exhibiting high color purity, visible-light-excitable property, and potential bioapplication.

An enantioselective deoxygenative functionalization of secondary amides with vinylpridines is developed by merging relay iridium catalysis and cooperative photoredox-chiral Bronsted acid catalysis, affording a series of valuable chiral amines in moderate to good yields with good enantioselectivities. The intriguing multiple catalytic system invoking triple-catalysis was found to be the key to the success of the current reactions, which may stimulate further development of catalytic methodologies for asymmetric deoxygenative transformations of amides.

The palladium-catalyzed highly regioselective asymmetric allylic alkylation of 3 '-indolyl-3-oxindole derivatives with Morita-Baylis-Hillman (MBH) carbonates was developed to facilely construct chiral 3,3'-bisindole derivatives under mild reaction conditions. The regioselectivity (alpha/gamma) of MBH carbonates was efficiently switched in the presence of chiral oxalamide phosphine or spiroketal-based diphosphine/Pd(0) complexes as a chiral catalyst. A series of multifunctional 3,3'-bisindole derivatives with all-carbon quaternary stereogenic centers were obtained in high yields with good to excellent enantio-, diastereo-, and regioselectivity. The present process is endowed with some salient features such as broad substrate scope, N-protecting group-free, excellent stereoselectivity, as well as adjustable regioselectivity.

Enantioselective construction of all-carbon quaternary centers has been achieved via the palladium-catalyzed highly enantioselective allenylation of oxindoles with 2,3-allenylic carbonates to afford a variety of optically active allene products, which contain oxindole units with different functional groups, in high ee. The corresponding synthetic applications have also been demonstrated.

Zwitterionic metal complexes of Rh and Ru featuring a tetraphenylborate ancillary ligand have been explored widely in organometallic chemistry. Analogous 3d metal complexes, however, are rarely known. From the oxidation reaction of cobalt(0)-N-heterocyclic carbene complexes [(NHC)Co(eta(2):eta(2)-(CH2CHSiMe2)(2)O)] (NHC = N-heterocyclic carbene) with [Cp2Fe][BPh4], we synthesized the zwitterionic cobalt(I)-NHC complexes [(IMes)Co((eta(6)-C6H5)BPh3)] (IMes = 1,3-bis(2,4,6-trimethylphenyl)-imidazole-2-ylidene, 1) and [(IPr)Co((eta(6)-C6H5)BPh3)] (IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazole-2-ylidene, 2) in good yields. Characterization data and computational studies revealed the S = 1 ground spin state for 1 and 2. These zwitterionic cobalt(I) complexes can act as cobalt(I) synthons to prepare cobalt(I)-NHC complexes bearing other ancillary ligands. Their reactions to CO and CNBut form the zwitterionic cobalt(I) complexes [(IMes)Co((eta(6)-C6H5)BPh3)(CO)] (3), [(IPr)Co((eta(6)-C6H5)BPh3)(CO)] (4), and [(IMes)Co((eta(6)-C6H5)BPh3)(CNBut)] (5) and the ionic cobalt(I) complex [(IMes)Co(CNBut)(4)][BPh4] (6). In the reactions of 2 with pyridine, IPr, and IMes, the ionic cobalt(I)-NHC complexes [(IPr)Co(py)(3)][BPh4] (7), [(IPr)(2)Co][BPh4] (8) and [(IPr)Co(IMes)][BPh4] (9) were formed. The structures of these complexes were established by single-crystal X-ray diffraction studies.

The trifluoromethylsulfinylation reaction of activated arenes with trifluoromethanesulfinyl chloride (CF3SOCl) in the presence of Lewis acid was achieved under mild and solvent-free conditions. A series of aryl trifluoromethyl sulfoxides were obtained in moderate to high yields. The protocol could be extended to the perfluoroalkylsulfinylation of activated arenes, as well as the trifluoromethylsulfinylation of indoles without additive. A facile method for the trifluoromethylsulfinylation of activated arenes with trifluoromethanesulfinyl chloride in the presence of Lewis acid was developed. The protocol could be expanded to the perfluoroalkylsulfinylation of activated arenes, as well as the trifluoromethylsulfinylation of indoles without additive. image

Rationale: Recently N-Fluoroarenesulfonamides (ArSO2NHF) were found to be promising precursors for the preparation of N-fluorobenzenesulfonimide derivatives without applying F-2. 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 ArSO2NH2. 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-.

Esophageal squamous cell carcinoma (ESCC) remains an important health concern in developing countries. Patients with advanced ESCC have a poor prognosis and survival rate, and achieving early diagnosis remains a challenge. Metabolic biomarkers are gradually gaining attention as early diagnostic biomarkers. Hence, this multicenter study comprehensively evaluated metabolism dysregulation in ESCC through an integrated research strategy to identify key metabolite biomarkers of ESCC. First, the metabolic profiles were examined in tissue and serum samples from the discovery cohort (n = 162; ESCC patients, n = 81; healthy volunteers, n = 81), and ESCC tissue-induced metabolite alterations were observed in the serum. Afterward, RNA sequencing of tissue samples (n = 46) was performed, followed by an integrated analysis of metabolomics and transcriptomics. The potential biomarkers for ESCC were further identified by censoring gene-metabolite regulatory networks. The diagnostic value of the identified biomarkers was validated in a validation cohort (n = 220), and the biological function was verified. A total of 457 dysregulated metabolites were identified in the serum, of which 36 were induced by tumor tissues. The integrated analyses revealed significant alterations in the purine salvage pathway, wherein the abundance of hypoxanthine/xanthine exhibited a positive correlation with HPRT1 expression and tumor size. A diagnostic model was developed using two purine salvage-associated metabolites. This model could accurately discriminate patients with ESCC from normal individuals, with an area under the curve (AUC) (95% confidence interval (CI): 0.680-0.843) of 0.765 in the external cohort. Hypoxanthine and HPRT1 exerted a synergistic effect in terms of promoting ESCC progression. These findings are anticipated to provide valuable support in developing novel diagnostic approaches for early ESCC and enhance our comprehension of the metabolic mechanisms underlying this disease.