CO₂‑Promoted and Nickel-Catalyzed Direct Hydroallylation of Terminal Alkynes with Allylic Alcohols: Access to 1,4-Dienes

CO2-promoted and Ni-catalyzed direct hydroallylation of terminal alkynes with allylic alcohols has been achieved. Various 1,4-dienes could be synthesized in good yield with excellent Markovnikov selectivity for alkyl- and aryl-substituted terminal alkynes under mild reaction conditions. A gram-scale reaction gives considerable yield. Preliminary mechanistic studies support the reaction pathway through sequential carboxylation/allylnickelation/lithium bicarbonate nickelation/transmetalation in the hydroallylation of alkynes with allylic alcohols in the presence of CO2

Visible-Light-Driven Reductive Carboxylation of Benzyl Bromides with Carbon Dioxide Using Formate as Terminal Reductant

Cheap and available formate can be seen formally as a carbon dioxide radical anion (CO2•–) combined with a hydrogen atom, where the CO2•– is not only a highly active radical but also a very powerful reductant. In this paper, we successfully realized a visible-light-driven carboxylation of benzyl bromides with carbon dioxide to prepare high-value arylacetic acids using potassium formate as a terminal reductant. This reaction is characterized by mild reaction conditions and a wide range of substrates. Moreover, under nitrogen atmosphere, the reaction can also achieve the carboxylation of benzyl bromides utilizing an excess of potassium formate. Mechanistic experiments indicate this carboxylation proceeded through CO2•–, which was generated from the oxidation of 1,4-diazabicyclo[2.2.2]­octane with excited photosensitizer Ir­(ppy)2(dtbbpy)­PF6 in the presence of the potassium formate

Table1_Characterization of cuproptosis in gastric cancer and relationship with clinical and drug reactions.DOCX

Gastric cancer (GC) is the fifth most common cancer worldwide. Cuproptosis is associated with cell growth and death as well as tumorigenesis. Aiming to lucubrate the potential influence of CRGs in gastric cancer, we acquired datasets of gastric cancer patients from TCGA and GEO. The identification of molecular subtypes with CRGs expression was achieved through unsupervised learning-cluster analysis. To evaluate the application value of subtypes, the K-M survival analysis was conducted to evaluate the clinical prognostic characteristics. Subsequently, we performed Gene Set Variation Analysis (GSVA) and utilized ssGSEA to quantify the extent of immune infiltration. Further, the K-M survival analysis was used to identify the prognosis-related CRGs. Next, signature genes of diagnostic predictive value were screened using the least absolute shrinkage and selection operator (LASSO) algorithm from the expression matrix for TCGA, as well as the signature gene-related subtype was clustered by the “ConsensusClusterPlus” package. Finally, the immunological and drug sensitivity assessments of the signature gene-related subtypes were conducted. A total of 173 CRGs were identified, most of the CRGs undergo copy number variation in gastric cancer. Under different patient subtypes, immune cell levels differed significantly, and the subtype exhibiting high expression of the CRGs had a better prognosis. Furthermore, we selected 34 CRGs that were highly correlated with the prognosis of gastric cancer. By constructing a multivariate Cox proportional-hazards model and a hazard scoring system, we were able to categorize patients into high- and low-risk groups based on their hazard score. K-M analysis demonstrated a significant survival disadvantage in the high-risk group. Based on Lasso regression analysis, we screened 16 signature genes, a multivariate logistic regression model [cutoff: 0.149 (0.000, 0.974), AUC:0.987] and a prognosis network diagram was constructed and their prediction efficiency for gastric cancer prognostic diagnosis was well validated. According to the signature genes, the patients were separated to two signature subtypes. We found that patients with higher CRGs expression and better prognosis had lower levels of immune infiltration. Finally, according to the results of drug susceptibility analysis, docetaxel, 5-Fluorouracil, gemcitabin, and paclitaxel were found to be more sensitive to gastric cancer.</p