The rational design based on a deep understanding of the present reaction mechanism is an important, viable approach to discover new organic transformations. β-Hydrogen elimination from palladium complexes is a fundamental reaction in palladium catalysis. Normally, the eliminated β-hydrogen has to be attached to a sp³-carbon. We envision that the hydrogen elimination from sp²-carbon is possible by using thoroughly designed reaction systems, which may offer a new strategy for the preparation of allenes. Here, we describe a palladium-catalyzed cross-coupling of 2,2-diarylvinyl bromides and diazo compounds, where a β-vinylic hydrogen elimination from allylic palladium intermediate is proposed to be the key step. Both aryl diazo carbonyl compounds and N-tosylhydrazones are competent carbene precursors in this reaction. The reaction mechanism is explored by control experiments, KIE studies and DFT calculations.

The utility of adding ion mobility (IM) to quadrupole time of flight mass spectrometry (IM-QTOF MS) for highly effective analysis of multiple pesticides in complex matrices was evaluated. Based on an in-house IM-MS database, the identification was performed through the match of the protonated ion ([M + H]⁺) and the CCS value. Moreover, the structural confirmation was achieved by using the accurate masses of [M + H]⁺ with its fragment ions, and the reference CCS value. The method did not require chromatographic separation and the analysis time of each measurement cycle is 1.6 min. The “cleaned” IM-MS spectra afforded by the drift time filtration improved the reliability of structural confirmation. As a result, the limit of detection (LOD) of 92% of test pesticides under the APCI mode and 58% of test pesticides under the ESI mode spiked in scallion was not more than 20 ng mL⁻¹. In the analysis of practical samples, the identification of pyrimethanil was confirmed in celery, and benalaxyl and tebuconazole were identified as false positives in scallion. The time-saving, extended-scope and high-throughput method described in this work is capable of determining multiple pesticide residues in complex matrices with high sensitivity for monitoring applications.

In this work, a new pyrylium derivatization-assisted liquid chromatography-mass spectrometry (LC-MS) method was developed for metabolite profiling of the glutathione anabolic pathway (GAP) in cancer tissues and cells. The pyrylium salt of 6,7-dimethoxy-3-methyl isochromenylium tetrafluoroborate (DMMIC) was used to label the amino group of metabolites, and a reductant of dithiothreitol (DTT) was employed to stabilize the thiol group. By combining DMMIC derivatization with LC-MS, it was feasible to quantify the 13 main metabolites on the GAP in complex biological samples, which had good linearity (R² = 0.9981−0.9999), precision (interday precision of 1.6%–19.0% and intraday precision of 1.4%–19.8%) and accuracy (83.4%–115.7%). Moreover, the recovery assessments in tissues (82.5%–107.3%) and in cells (98.1%–118.9%) with GSH-¹³C2, ¹⁵N, and Cys-¹⁵N demonstrated the reliability of the method in detecting tissues and cells. Following a methodological evaluation, the method was applied successfully to investigate difference in the GAP between the carcinoma and para-carcinoma tissues of esophageal squamous cell carcinoma (ESCC) and the effect of p-hydroxycinnamaldehyde (CMSP) on the GAP in KYSE-150 esophageal cancer cells. The results demonstrate that the developed method provides a promising new tool to elucidate the roles of GAP in physiological and pathological processes, which can contribute to research on drugs and diseases.