31 research outputs found

    Cobalt-Catalyzed Enantioselective Intramolecular Hydroacylation of Ketones and Olefins

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    Cobalt–chiral diphoshine catalytic systems promote intramolecular hydroacylation reactions of 2-acylbenzaldehydes and 2-alkenylbenzaldehydes to afford phthalide and indanone derivatives, respectively, in moderate to good yields with high enantioselectivities. The ketone hydroacylation did not exhibit a significant H/D kinetic isotope effect (KIE) with respect to the aldehyde C–H bond, indicating that C–H activation would not be involved in the rate-limiting step

    Cobalt-Catalyzed Intermolecular Hydroacylation of Olefins through Chelation-Assisted Imidoyl C–H Activation

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    A low-valent cobalt catalyst generated from cobalt­(II) bromide, a diphosphine ligand, and zinc powder promotes intermolecular hydroacylation of olefins using <i>N</i>-3-picolin-2-yl aldimines as aldehyde equivalents, which affords, upon acidic hydrolysis, ketone products in moderate to good yields with high linear selectivity. The reaction is applicable to styrenes, vinylsilanes, and aliphatic olefins as well as to various aryl and heteroaryl aldimines. The cobalt catalysis features a distinctively lower reaction temperature (60 °C) compared with those required for the same type of transformations catalyzed by rhodium complexes (typically 130–150 °C)

    Image_1_The prognosis of bladder cancer is affected by fatty acid metabolism, inflammation, and hypoxia.tif

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    BackgroundThe prognosis of bladder cancer (BC) is poor, and there is no effective personalized management method for BC patients at present. Developing an accurate model is helpful to make treatment plan and prognosis analysis for BC patients. Endogenous fatty acid metabolism causes cancer cells to become hypoxic, and the coexistence of hypoxia and inflammation is often characteristic of cancer. All three together influence the tumor immune microenvironment, treatment, and prognosis of BC.MethodsWe used The Cancer Genome Atlas-Bladder Urothelial Carcinoma (TCGA-BLAC) cohorts as a train group to build a risk model based on fatty acid metabolism, hypoxia and inflammation-related gene signatures and performed external validation with GSE13507, GSE31684, and GSE39281 cohorts. We validated the model to correlate with the clinicopathological characteristics of patients, created an accuracy nomogram, and explored the differences in immune microenvironment and enrichment pathways.ResultsWe found significant differences in overall survival and progression-free survival between high- and low-risk groups, and patients in the low-risk group had a better prognosis than those in the high-risk group. In the train group, the AUCs for predicting overall survival at 1, 3, and 5 years were 0.745, 0.712, and 0.729, respectively. The 1-, 3-, and 5-year overall survival AUCs were 0.589, 0.672, and 0.666 in the external validation group, respectively. The risk score independently predicted the prognosis of BC patients with AUCs of 0.729. In addition, there was a significant correlation between risk scores and BC clinicopathological features and, in the GSE13507 cohort, we observed that BC progression and deeper invasion were associated with higher risk scores. Risk scores were highly correlated with coproptosis, pyroptosis, m7G, immune checkpoint-related genes, and immune microenvironment. In addition, we found that patients in the low-risk group responded better to immunotherapy, whereas patients in the high-risk group were more sensitive to commonly used chemotherapy drugs.ConclusionOur findings provide new treatment decisions for BC, and can effectively predict the prognosis of BC patients, which is helpful for the management of BC patients.</p

    Image_6_The prognosis of bladder cancer is affected by fatty acid metabolism, inflammation, and hypoxia.tif

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    BackgroundThe prognosis of bladder cancer (BC) is poor, and there is no effective personalized management method for BC patients at present. Developing an accurate model is helpful to make treatment plan and prognosis analysis for BC patients. Endogenous fatty acid metabolism causes cancer cells to become hypoxic, and the coexistence of hypoxia and inflammation is often characteristic of cancer. All three together influence the tumor immune microenvironment, treatment, and prognosis of BC.MethodsWe used The Cancer Genome Atlas-Bladder Urothelial Carcinoma (TCGA-BLAC) cohorts as a train group to build a risk model based on fatty acid metabolism, hypoxia and inflammation-related gene signatures and performed external validation with GSE13507, GSE31684, and GSE39281 cohorts. We validated the model to correlate with the clinicopathological characteristics of patients, created an accuracy nomogram, and explored the differences in immune microenvironment and enrichment pathways.ResultsWe found significant differences in overall survival and progression-free survival between high- and low-risk groups, and patients in the low-risk group had a better prognosis than those in the high-risk group. In the train group, the AUCs for predicting overall survival at 1, 3, and 5 years were 0.745, 0.712, and 0.729, respectively. The 1-, 3-, and 5-year overall survival AUCs were 0.589, 0.672, and 0.666 in the external validation group, respectively. The risk score independently predicted the prognosis of BC patients with AUCs of 0.729. In addition, there was a significant correlation between risk scores and BC clinicopathological features and, in the GSE13507 cohort, we observed that BC progression and deeper invasion were associated with higher risk scores. Risk scores were highly correlated with coproptosis, pyroptosis, m7G, immune checkpoint-related genes, and immune microenvironment. In addition, we found that patients in the low-risk group responded better to immunotherapy, whereas patients in the high-risk group were more sensitive to commonly used chemotherapy drugs.ConclusionOur findings provide new treatment decisions for BC, and can effectively predict the prognosis of BC patients, which is helpful for the management of BC patients.</p

    Image_3_The prognosis of bladder cancer is affected by fatty acid metabolism, inflammation, and hypoxia.tif

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    BackgroundThe prognosis of bladder cancer (BC) is poor, and there is no effective personalized management method for BC patients at present. Developing an accurate model is helpful to make treatment plan and prognosis analysis for BC patients. Endogenous fatty acid metabolism causes cancer cells to become hypoxic, and the coexistence of hypoxia and inflammation is often characteristic of cancer. All three together influence the tumor immune microenvironment, treatment, and prognosis of BC.MethodsWe used The Cancer Genome Atlas-Bladder Urothelial Carcinoma (TCGA-BLAC) cohorts as a train group to build a risk model based on fatty acid metabolism, hypoxia and inflammation-related gene signatures and performed external validation with GSE13507, GSE31684, and GSE39281 cohorts. We validated the model to correlate with the clinicopathological characteristics of patients, created an accuracy nomogram, and explored the differences in immune microenvironment and enrichment pathways.ResultsWe found significant differences in overall survival and progression-free survival between high- and low-risk groups, and patients in the low-risk group had a better prognosis than those in the high-risk group. In the train group, the AUCs for predicting overall survival at 1, 3, and 5 years were 0.745, 0.712, and 0.729, respectively. The 1-, 3-, and 5-year overall survival AUCs were 0.589, 0.672, and 0.666 in the external validation group, respectively. The risk score independently predicted the prognosis of BC patients with AUCs of 0.729. In addition, there was a significant correlation between risk scores and BC clinicopathological features and, in the GSE13507 cohort, we observed that BC progression and deeper invasion were associated with higher risk scores. Risk scores were highly correlated with coproptosis, pyroptosis, m7G, immune checkpoint-related genes, and immune microenvironment. In addition, we found that patients in the low-risk group responded better to immunotherapy, whereas patients in the high-risk group were more sensitive to commonly used chemotherapy drugs.ConclusionOur findings provide new treatment decisions for BC, and can effectively predict the prognosis of BC patients, which is helpful for the management of BC patients.</p

    Image_5_The prognosis of bladder cancer is affected by fatty acid metabolism, inflammation, and hypoxia.tif

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    BackgroundThe prognosis of bladder cancer (BC) is poor, and there is no effective personalized management method for BC patients at present. Developing an accurate model is helpful to make treatment plan and prognosis analysis for BC patients. Endogenous fatty acid metabolism causes cancer cells to become hypoxic, and the coexistence of hypoxia and inflammation is often characteristic of cancer. All three together influence the tumor immune microenvironment, treatment, and prognosis of BC.MethodsWe used The Cancer Genome Atlas-Bladder Urothelial Carcinoma (TCGA-BLAC) cohorts as a train group to build a risk model based on fatty acid metabolism, hypoxia and inflammation-related gene signatures and performed external validation with GSE13507, GSE31684, and GSE39281 cohorts. We validated the model to correlate with the clinicopathological characteristics of patients, created an accuracy nomogram, and explored the differences in immune microenvironment and enrichment pathways.ResultsWe found significant differences in overall survival and progression-free survival between high- and low-risk groups, and patients in the low-risk group had a better prognosis than those in the high-risk group. In the train group, the AUCs for predicting overall survival at 1, 3, and 5 years were 0.745, 0.712, and 0.729, respectively. The 1-, 3-, and 5-year overall survival AUCs were 0.589, 0.672, and 0.666 in the external validation group, respectively. The risk score independently predicted the prognosis of BC patients with AUCs of 0.729. In addition, there was a significant correlation between risk scores and BC clinicopathological features and, in the GSE13507 cohort, we observed that BC progression and deeper invasion were associated with higher risk scores. Risk scores were highly correlated with coproptosis, pyroptosis, m7G, immune checkpoint-related genes, and immune microenvironment. In addition, we found that patients in the low-risk group responded better to immunotherapy, whereas patients in the high-risk group were more sensitive to commonly used chemotherapy drugs.ConclusionOur findings provide new treatment decisions for BC, and can effectively predict the prognosis of BC patients, which is helpful for the management of BC patients.</p

    Image_2_The prognosis of bladder cancer is affected by fatty acid metabolism, inflammation, and hypoxia.tif

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    BackgroundThe prognosis of bladder cancer (BC) is poor, and there is no effective personalized management method for BC patients at present. Developing an accurate model is helpful to make treatment plan and prognosis analysis for BC patients. Endogenous fatty acid metabolism causes cancer cells to become hypoxic, and the coexistence of hypoxia and inflammation is often characteristic of cancer. All three together influence the tumor immune microenvironment, treatment, and prognosis of BC.MethodsWe used The Cancer Genome Atlas-Bladder Urothelial Carcinoma (TCGA-BLAC) cohorts as a train group to build a risk model based on fatty acid metabolism, hypoxia and inflammation-related gene signatures and performed external validation with GSE13507, GSE31684, and GSE39281 cohorts. We validated the model to correlate with the clinicopathological characteristics of patients, created an accuracy nomogram, and explored the differences in immune microenvironment and enrichment pathways.ResultsWe found significant differences in overall survival and progression-free survival between high- and low-risk groups, and patients in the low-risk group had a better prognosis than those in the high-risk group. In the train group, the AUCs for predicting overall survival at 1, 3, and 5 years were 0.745, 0.712, and 0.729, respectively. The 1-, 3-, and 5-year overall survival AUCs were 0.589, 0.672, and 0.666 in the external validation group, respectively. The risk score independently predicted the prognosis of BC patients with AUCs of 0.729. In addition, there was a significant correlation between risk scores and BC clinicopathological features and, in the GSE13507 cohort, we observed that BC progression and deeper invasion were associated with higher risk scores. Risk scores were highly correlated with coproptosis, pyroptosis, m7G, immune checkpoint-related genes, and immune microenvironment. In addition, we found that patients in the low-risk group responded better to immunotherapy, whereas patients in the high-risk group were more sensitive to commonly used chemotherapy drugs.ConclusionOur findings provide new treatment decisions for BC, and can effectively predict the prognosis of BC patients, which is helpful for the management of BC patients.</p

    Image_4_The prognosis of bladder cancer is affected by fatty acid metabolism, inflammation, and hypoxia.tif

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    BackgroundThe prognosis of bladder cancer (BC) is poor, and there is no effective personalized management method for BC patients at present. Developing an accurate model is helpful to make treatment plan and prognosis analysis for BC patients. Endogenous fatty acid metabolism causes cancer cells to become hypoxic, and the coexistence of hypoxia and inflammation is often characteristic of cancer. All three together influence the tumor immune microenvironment, treatment, and prognosis of BC.MethodsWe used The Cancer Genome Atlas-Bladder Urothelial Carcinoma (TCGA-BLAC) cohorts as a train group to build a risk model based on fatty acid metabolism, hypoxia and inflammation-related gene signatures and performed external validation with GSE13507, GSE31684, and GSE39281 cohorts. We validated the model to correlate with the clinicopathological characteristics of patients, created an accuracy nomogram, and explored the differences in immune microenvironment and enrichment pathways.ResultsWe found significant differences in overall survival and progression-free survival between high- and low-risk groups, and patients in the low-risk group had a better prognosis than those in the high-risk group. In the train group, the AUCs for predicting overall survival at 1, 3, and 5 years were 0.745, 0.712, and 0.729, respectively. The 1-, 3-, and 5-year overall survival AUCs were 0.589, 0.672, and 0.666 in the external validation group, respectively. The risk score independently predicted the prognosis of BC patients with AUCs of 0.729. In addition, there was a significant correlation between risk scores and BC clinicopathological features and, in the GSE13507 cohort, we observed that BC progression and deeper invasion were associated with higher risk scores. Risk scores were highly correlated with coproptosis, pyroptosis, m7G, immune checkpoint-related genes, and immune microenvironment. In addition, we found that patients in the low-risk group responded better to immunotherapy, whereas patients in the high-risk group were more sensitive to commonly used chemotherapy drugs.ConclusionOur findings provide new treatment decisions for BC, and can effectively predict the prognosis of BC patients, which is helpful for the management of BC patients.</p

    DataSheet_1_The prognosis of bladder cancer is affected by fatty acid metabolism, inflammation, and hypoxia.docx

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    BackgroundThe prognosis of bladder cancer (BC) is poor, and there is no effective personalized management method for BC patients at present. Developing an accurate model is helpful to make treatment plan and prognosis analysis for BC patients. Endogenous fatty acid metabolism causes cancer cells to become hypoxic, and the coexistence of hypoxia and inflammation is often characteristic of cancer. All three together influence the tumor immune microenvironment, treatment, and prognosis of BC.MethodsWe used The Cancer Genome Atlas-Bladder Urothelial Carcinoma (TCGA-BLAC) cohorts as a train group to build a risk model based on fatty acid metabolism, hypoxia and inflammation-related gene signatures and performed external validation with GSE13507, GSE31684, and GSE39281 cohorts. We validated the model to correlate with the clinicopathological characteristics of patients, created an accuracy nomogram, and explored the differences in immune microenvironment and enrichment pathways.ResultsWe found significant differences in overall survival and progression-free survival between high- and low-risk groups, and patients in the low-risk group had a better prognosis than those in the high-risk group. In the train group, the AUCs for predicting overall survival at 1, 3, and 5 years were 0.745, 0.712, and 0.729, respectively. The 1-, 3-, and 5-year overall survival AUCs were 0.589, 0.672, and 0.666 in the external validation group, respectively. The risk score independently predicted the prognosis of BC patients with AUCs of 0.729. In addition, there was a significant correlation between risk scores and BC clinicopathological features and, in the GSE13507 cohort, we observed that BC progression and deeper invasion were associated with higher risk scores. Risk scores were highly correlated with coproptosis, pyroptosis, m7G, immune checkpoint-related genes, and immune microenvironment. In addition, we found that patients in the low-risk group responded better to immunotherapy, whereas patients in the high-risk group were more sensitive to commonly used chemotherapy drugs.ConclusionOur findings provide new treatment decisions for BC, and can effectively predict the prognosis of BC patients, which is helpful for the management of BC patients.</p

    Catalytic Asymmetric Synthesis of Tröger’s Base Analogues with Nitrogen Stereocenter

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    Nitrogen stereocenters are common chiral units in natural products, pharmaceuticals, and chiral catalysts. However, their research has lagged largely behind, compared with carbon stereocenters and other heteroatom stereocenters. Herein, we report an efficient method for the catalytic asymmetric synthesis of Tröger’s base analogues with nitrogen stereocenters via palladium catalysis and home-developed GF-Phos. It allows rapid construction of a new rigid cleft-like structure with both a C- and a N-stereogenic center in high efficiency and selectivity. A variety of applications as a chiral organocatalyst and metallic catalyst precursors were demonstrated. Furthermore, DFT calculations suggest that the NH···O hydrogen bonding and weak interaction between the substrate and ligand are crucial for the excellent enantioselectivity control
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