A synthetic method has been developed for the synthesis of unsymmetrical ferrocene aryl chalcogenides by C-H activation of ferroceneamide using 8-aminoquinoline as a directing group, aryl dichalcogenides, and copper(II) catalyst in the presence of silver acetate oxidant at 80 °C in DMSO. The developed methodology is quite general and mild to access three unsymmetrical diaryl chalcogenides (sulfide, selenide, and telluride) and also amenable to aryl dichalcogenides with sensitive bromo, chloro, and nitro functionalities. Further, ferrocene aryl tellurides have been obtained in moderate yields for the first time by the developed C-H activation approach. In the mechanistic part, it seems that the presence of a rigid chelating directing ligand is crucial for the aryl chalcogenation reaction of C-H bond under copper catalysis as the nonrigid bidentate directing ligands were unsuccessful for the transformation.
Neoadjuvant immunotherapy has the potential to decrease the risk of hepatocellular carcinoma (HCC) recurrence post resection. The objectives of this study were to assess the value of pre-treatment MRI parameters for prediction of HCC immunophenotype and response in a cohort of patients undergoing neoadjuvant immunotherapy prior to liver resection. We hypothesize that diffusion and perfusion MRI can predict HCC response to neoadjuvant immunotherapy. It was observed that abundant of TILs decreases ADC in tumors. Moreover, uptake rate is higher in highly necrotic tumors.
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