Divergent Total Synthesis of Triptolide, Triptonide, Tripdiolide, 16-Hydroxytriptolide, and Their Analogues

A divergent route was developed for the formal total synthesis of triptolide, triptonide, and tripdiolide, as well as a total synthesis of 16-hydroxytriptolide and their analogues in an enantioselective form. Common advanced intermediate 5 was concisely assembled by employing an indium­(III)-catalyzed cationic polycyclization reaction and a palladium-catalyzed carbonylation–lactone formation reaction as key steps. This advanced intermediate was readily converted to the above natural products by using palladium-catalyzed cross-coupling or the Claisen rearrangement reaction as key steps. Additionally, preliminary structure–cytotoxic activity relationship studies of C13 suggested that it might be a new modification site that could still retain the cytotoxicity

Divergent Total Synthesis of Triptolide, Triptonide, Tripdiolide, 16-Hydroxytriptolide, and Their Analogues

A divergent route was developed for the formal total synthesis of triptolide, triptonide, and tripdiolide, as well as a total synthesis of 16-hydroxytriptolide and their analogues in an enantioselective form. Common advanced intermediate <b>5</b> was concisely assembled by employing an indium­(III)-catalyzed cationic polycyclization reaction and a palladium-catalyzed carbonylation–lactone formation reaction as key steps. This advanced intermediate was readily converted to the above natural products by using palladium-catalyzed cross-coupling or the Claisen rearrangement reaction as key steps. Additionally, preliminary structure–cytotoxic activity relationship studies of C13 suggested that it might be a new modification site that could still retain the cytotoxicity

Divergent Total Synthesis of Triptolide, Triptonide, Tripdiolide, 16-Hydroxytriptolide, and Their Analogues

A divergent route was developed for the formal total synthesis of triptolide, triptonide, and tripdiolide, as well as a total synthesis of 16-hydroxytriptolide and their analogues in an enantioselective form. Common advanced intermediate <b>5</b> was concisely assembled by employing an indium­(III)-catalyzed cationic polycyclization reaction and a palladium-catalyzed carbonylation–lactone formation reaction as key steps. This advanced intermediate was readily converted to the above natural products by using palladium-catalyzed cross-coupling or the Claisen rearrangement reaction as key steps. Additionally, preliminary structure–cytotoxic activity relationship studies of C13 suggested that it might be a new modification site that could still retain the cytotoxicity

Rhodium-Catalyzed Direct Addition of Aryl C–H Bonds to Nitrosobenzenes at Room Temperature

An unprecedented Rh-catalyzed direct addition of aryl C–H bonds to nitrosobenzenes has been developed under very mild reaction conditions (room temperature). The reaction is highly step-, atom-, and redox-economic and compatible with air and water to <i>N</i>-selectively provide a variety of <i>N</i>-diarylhydroxylamines in good to excellent yields. More importantly, this process may provide a new direction for C–N bond formation through direct C(sp²)–H functionalization

Table_1_PANoptosis-related genes function as efficient prognostic biomarkers in colon adenocarcinoma.csv

BackgroundPANoptosis is a newly discovered cell death type, and tightly associated with immune system activities. To date, the mechanism, regulation and application of PANoptosis in tumor is largely unknown. Our aim is to explore the prognostic value of PANoptosis-related genes in colon adenocarcinoma (COAD).MethodsAnalyzing data from The Cancer Genome Atlas-COAD (TCGA-COAD) involving 458 COAD cases, we concentrated on five PANoptosis pathways from the Molecular Signatures Database (MSigDB) and a comprehensive set of immune-related genes. Our approach involved identifying distinct genetic COAD subtype clusters and developing a prognostic model based on these parameters.ResultsThe research successfully identified two genetic subtype clusters in COAD, marked by distinct profiles in PANoptosis pathways and immune-related gene expression. A prognostic model, incorporating these findings, demonstrated significant predictive power for survival outcomes, underscoring the interplay between PANoptosis and immune responses in COAD.ConclusionThis study enhances our understanding of COAD’s genetic framework, emphasizing the synergy between cell death pathways and the immune system. The development of a prognostic model based on these insights offers a promising tool for personalized treatment strategies. Future research should focus on validating and refining this model in clinical settings to optimize therapeutic interventions in COAD.</p

Rh(III)-Catalyzed Addition of Alkenyl C–H Bond to Isocyanates and Intramolecular Cyclization: Direct Synthesis 5‑Ylidenepyrrol-2(5<i>H</i>)‑ones

The rhodium-catalyzed addition of an alkenyl C–H bond to isocyanates via sp² C–H bond activation followed by an intramolecular cyclization is described. This atom-economic and catalytic reaction affords a simple and straightforward access to biologically relevant 5-ylidene pyrrol-2(5<i>H</i>)-ones and can be carried out under mild and neutral conditions in the absence of any additives and environmentally hazardous waste production

Copper(I)-Catalyzed Aryl or Vinyl Addition to Electron-Deficient Alkenes Cascaded by Cationic Cyclization

An exoselective copper-catalyzed arylation– and vinylation–carbocyclization of electron-deficient alkenes was developed to provide rapid and efficient access to a variety of functionalized 3,3-disubstituted oxindoles. With this method, a highly efficient and concise formal synthesis of (±)-physostigmine and (±)-physovenine has been completed

Rh(III)-Catalyzed C–H Amidation with <i>N</i>‑Hydroxycarbamates: A New Entry to <i>N</i>‑Carbamate-Protected Arylamines

An unprecedented Rh­(III)-catalyzed direct intermolecular C–H amidation with <i>N</i>-hydroxycarbamates has been developed. Different directing groups, such as pyridine, pyrimidine, pyrazole, and <i>N</i>-OMe oxime, can be employed in this C–H amidation process, providing valuable <i>N</i>-carbamate-protected arylamines (e.g., Cbz, Moz, Ac, Boc, and Fmoc). More importantly, this process may afford a new avenue for intermolecular C–H amidation where readily available <i>N</i>-hydroxycarbamates can be used as the nitrogen sourc

DataSheet1_Analysis of the correlation between non-alcoholic fatty liver disease and the risk of colorectal neoplasms.docx

This study aims at assessing the potential association between non-alcoholic fatty liver disease (NAFLD) and colorectal neoplasms (CRN). PubMed, Cochrane Library, and Embase were searched for cohort studies. 14 cohort studies with a total population of 38,761,773 were included for meta-analysis after selection. The results showed that NAFLD is related to an increased risk of CRN (OR = 1.23; 95% CI: 1.14–1.32; I2 = 70.7%, p 2 = 66.4%) and colorectal cancer (CRC) (OR = 1.13; 95% CI = 1.12–1.15; I2 = 69.4%). There is no close correlation between smoking status of NAFLD patients and CRN. Interestingly, bioinformatics analysis revealed that there were overlap of dysregulated gene sets among NAFLD, CRC, and two recently identified regulated cell death types, ferroptosis and cuproptosis, respectively. Our meta- and bioinformatics analysis shows that NAFLD increases the risk of CRN. Ferroptosis and cuproptosis may be the critical links between NAFLD and CRN, respectively. These findings here support that NAFLD is necessary to be considered as an emerging risk factor for CRN.</p

Rh(III)-Catalyzed C–H Amidation with <i>N</i>‑Hydroxycarbamates: A New Entry to <i>N</i>‑Carbamate-Protected Arylamines

An unprecedented Rh­(III)-catalyzed direct intermolecular C–H amidation with <i>N</i>-hydroxycarbamates has been developed. Different directing groups, such as pyridine, pyrimidine, pyrazole, and <i>N</i>-OMe oxime, can be employed in this C–H amidation process, providing valuable <i>N</i>-carbamate-protected arylamines (e.g., Cbz, Moz, Ac, Boc, and Fmoc). More importantly, this process may afford a new avenue for intermolecular C–H amidation where readily available <i>N</i>-hydroxycarbamates can be used as the nitrogen sourc