Selective Electrochemical Oxidation of Benzylic C-H to Benzylic Alcohols with the Aid of Imidazolium Radical Mediators.

Selective oxidation of benzylic C-H to benzylic alcohols is a well-known challenge in the chemical community since benzylic C-H is more prone to be overoxidized to benzylic ketones. In this work, we report the highly selective electro-oxidation of benzylic C-H to benzylic alcohols in an undivided cell in ionic liquid-based solution. As an example, the selectivity toward xanthydrol could be as high as 95.7% at complete conversion of xanthene, a typical benzylic C-H compound, on gram-scale in imidazolium bromide/H2O/DMF. Mechanism investigation reveals that the imidazolium radical generated in situ participants in a proton-coupled electron transfer process and low-barrier hydrogen bonds stabilize the reaction intermediates, together steering the redox equilibrium, favoring benzylic alcohols over benzylic ketones.

Identification of Immune-Related Subtypes and Characterization of Tumor Microenvironment Infiltration in Kidney Renal Clear Cell Carcinoma.

Background: Tumor microenvironment (TME) plays indisputable role in the progression of cancers. Immune cell infiltration (ICI) in TME was related to the prognosis of tumor patients. In this paper, we identified the pattern of immune-related ICI subtypes based on the TME immune infiltration pattern. Methods: The data from kidney renal clear cell carcinoma data (KIRC) was downloaded from the TCGA database. The distinct ICI subtypes were identified using CIBERSORT and ESTIMATE algorithms. The gene subgroups were identified based on DEGs in ICI subtypes. The single sample gene set enrichment analysis (ssGSEA) was used to ascertain the ICI score. Kaplan-Meier curve with log-rank test was conducted to analyze the survival probability of patients with KIRC in different subtypes. Results: The patients with high ICI scores exhibited a longer survival time and lower expression of checkpoint-related and immune activity-related genes. The high ICI score clusters were positively related to TMB. The patients in the low TMB subgroups have a favorable prognosis. The prediction ICI score did not affect the TMB status, and the low TMB subgroups + low/high ICI score subgroups exhibited better survival. Conclusion: In all, the tumor immune microenvironment, ICI score, and TMB were important determinants of KIRC patients' survival outcomes. The TMB + ICI score may be a potential biomarker for predicting the prognosis of patients and for targeted immunotherapies to treating KIRC.