An efficient and controllable polyetherification of vinylethylene carbonate (VEC) using diols as initiators is developed. By using a synergistic catalysis with palladium and boron reagents under mild conditions, the polymerization process enables the regioselective production of a series of polyvinylethylene glycols (PVEGs) bearing pendent vinyl groups in high yields with accurate molecular weight control and narrow molecular weight distribution. The utility of PVEGs is demonstrated by the production of functional polyurethanes and post-polymerization modification thiol-ene photo-click chemistry.
View Article and Find Full Text PDFBackground: Hepatocellular carcinoma (HCC) is one of the most frequent cancers and the main cause of cancer-related death worldwide. Ectopic HCC, an extremely rare type of HCC, exhibits a wide range of clinical signs and radiographic features, making preoperative identification challenging.
Case Summary: A 47-year-old man underwent routine abdominal color ultrasonography, which identified an asymptomatic tumor in the left upper abdomen.
An efficient method for the enantioselective synthesis of 2,3-dihydrofurans bearing a quaternary stereocenter has been developed via Pd-catalyzed asymmetric allylic cycloaddition and a retro-Dieckmann Fragmentation cascade. The asymmetric allylic cycloaddition of vinylethylene carbonates with 3-cyanochromone followed by base-assisted retro-Dieckmann fragmentation proceeded smoothly via a one-pot process to produce chiral 3,4-disubstituted 2,3-dihydrofurans in high yields with excellent enantioselectivities.
View Article and Find Full Text PDFObjectives: This study was performed to investigate the relationship between right ventricular free wall longitudinal strain (RVFWSL) and low cardiac output syndrome (LCOS) after surgical aortic valve replacement (SAVR) and to further explore its association with readmission within 2 years in patients who developed LCOS after SAVR.
Methods: This single-center retrospective observational study involved consecutive patients who underwent SAVR at our hospital from May 2018 to June 2020. Preoperative echocardiography was obtained within 3 days before SAVR.
Background: Vascular endothelial dysfunction is regarded as an early event of hypertension. Galectin-3 (Gal-3) is known to participate in various pathological processes. Whilst previous studies showed that inhibition of Gal-3 effectively ameliorates angiotensin II (Ang II)-induced atherosclerosis or hypertension, it remains unclear whether Ang II regulates Gal-3 expression and actions in vascular endothelium.
View Article and Find Full Text PDFThe first enantioselective total synthesis of aryltetralin lignan acetals, (-)-formosanol, (+)-tsugacetal, (+)-methyl β-conidendral, and their enantiomers have been accomplished on the basis of the Pd-catalyzed asymmetric allylic cycloaddition as a key step. Six stereoisomers of the lignan acetals have been synthesized via a 7-8 step sequence in up to 14% overall yield. The cytotoxicity against several cancer cells has preliminarily been examined for the obtained six stereoisomers of lignan acetals.
View Article and Find Full Text PDFAn efficient method for the synthesis of functionalized chiral tetrahydrofuran (THF) acetals via Pd-catalyzed asymmetric allylic cycloaddition has been developed. With a palladium catalyst coordinated by a chiral phosphine ligand, the protocol is enabled to combine readily available vinyl epoxides and β-keto enol ethers to produce THF acetals bearing three stereocenters in a broad substrate scope with uniformly high levels of enantio- and diastereoselectivity.
View Article and Find Full Text PDF-Substituted 1,2,4-triazoles are ubiquitous skeletons in medicinal agents, agrochemicals, and organic materials. Herein, an efficient and practical method for the synthesis of -allylated 1,2,4-triazoles Pd-catalyzed allylic substitution of vinylethylene carbonates (VECs) with 1,2,4-triazoles has been developed. By using a catalyst generated from Pd(dba)·CHCl and DPPE under mild conditions, the process allows rapid access to -allylated 1,2,4-triazoles bearing diverse functionalities in high yields with excellent -selectivities, linear-selectivities, and -stereoselectivities.
View Article and Find Full Text PDFThe first Pd-catalyzed asymmetric three-component reaction of 2,3-allenol, aryl iodides, and 2-arylmethylenemolononitriles has been developed via an allenol carbopalladation and an allylic cycloaddition cascade. This process allows rapid access to substituted tetrahydrofurans bearing diverse functional groups in good yields with high diastereoselectivities and excellent enantioselectivities. The concise total synthesis of a lignan, (-)-2-episesaminone, has been achieved by the elaboration of a functionalized tetrahydrofuran obtained from this reaction.
View Article and Find Full Text PDFA new asymmetric catalytic protocol for the synthesis of enantioenriched -allyl 2-pyrodones has been developed via the first Pd-catalyzed regio- and enantioselective aminoarylation of allenols with aryl iodides and 2-pyridones. By using a palladium complex generated in situ from Pd(dba)·CHCl and (,,)-SKP as a catalyst, the three-component aminoarylation proceeded smoothly to afford a variety of functionalized -allylic 2-pyridones in high yields with good regioselectivities and excellent enantioselectivities.
View Article and Find Full Text PDFOvarian cancer is the most lethal gynecologic malignancy. Surgery and chemotherapy are the primary treatments for ovarian cancer; however, patients often succumb to recurrence with chemotherapeutic resistance within several years after the initial treatment. In the past two decades, immunotherapy has rapidly developed, and has revolutionized the treatment of various types of cancer.
View Article and Find Full Text PDFHerein, a practical and efficient approach to tetrahydrofurans with three-stereocenters has been developed through Pd-catalyzed asymmetric allylic cycloaddition of vinylethylene carbonates (VECs) with 2-nitroacrylates under mild conditions. By using this asymmetric catalytic reaction as a key step, several furofuran lignans with stereodivergency have been effectively synthesized through 5- or 6-step sequences from readily available starting materials.
View Article and Find Full Text PDFPd-catalyzed regio- and enantioselective allylic etherification of vinylethylene carbonates (VECs) with diols has been developed. By using cooperative catalysts of the chiral palladium complex and triethylborane in mild conditions, the process gave monoetherified and bisetherified polyglycol derivatives with tetrasubstituted stereocenters in high yields with complete regioselectivities and high levels of enantio- and diastereoselectivities.
View Article and Find Full Text PDFAn efficient method for the enantioselective synthesis of cyclic ureas has been developed through Pd-catalyzed asymmetric allylic cycloaddition of readily accessible nitrogen-containing allylic carbonates with isocyanates. By using a palladium complex in situ generated from Pd(dba)·CHCl and phosphoramidite or as a ligand under mild reaction conditions, the process afforded imidazolidinones and tetrahydropyrimidinones with high yields and high levels of enantioselectivities.
View Article and Find Full Text PDFA useful method for the enantioselective preparation of isoxazoline -oxides via Pd-catalyzed asymmetric allylic cycloaddition of nitro-containing allylic carbonates has been developed. By using palladium complex in situ generated from Pd(dba)·CHCl and phosphoramidite as a catalyst under mild conditions, the transformation afforded vinylated isoxazoline -oxides in high yields with acceptably high enantioselectivities.
View Article and Find Full Text PDFChem Commun (Camb)
October 2019
An efficient method for the asymmetric synthesis of N-substituted 2-pyridones via Pd-catalyzed regio- and enantioselective allylic substitution of hydroxyl-containing allylic carbonates with 2-pyridones has been developed. By using a palladium complex in situ generated from Pd2(dba)3·CHCl3 and phosphoramidite L2 as a ligand, the process allowed rapid access to N-substituted 2-pyridones with complete chemo- and regioselectivities and good to high enantioselectivities.
View Article and Find Full Text PDFAn efficient method for the construction of arylated allylic ethers was developed via three-component tandem arylation and allylic etherification of 2,3-allenol with aryl iodides and alcohols. In the cooperative catalytic system of a palladium complex and triethylborane, the process allows rapid access to functionalized 1-arylvinylated 1,2-diol derivatives in good to high yields with complete branch-selectivities. The synthetic utility of the present process was demonstrated by the late-stage functionalization of a drug molecule, the gram-scale synthesis and the elaboration of the products.
View Article and Find Full Text PDFObjective: The purpose of this study was to assess the fibrinolytic status after cardiopulmonary bypass in rheumatic valvular heart disease patients, and detect the associated factors of post-cardiopulmonary bypass hyperfibrinolysis.
Methods: According to the fibrinolytic status after cardiopulmonary bypass, 203 rheumatic valvular heart disease patients were divided into two groups: hyperfibrinolysis group (H group, n = 78) and non-hyperfibrinolysis group (NH group, n = 125). The demographic characteristics, operative variables, and postoperative follow-ups were compared between these two groups.
Background: Gastric cancer is one of the most common and deadly malignancies worldwide. Despite recent medical progress, the 5-year survival rate of gastric cancer is still unsatisfactory. 5-fluorouracil (5-Fu) is one of the first-line antineoplastic treatments for gastric cancer, as it can effectively induce cancer cell apoptosis.
View Article and Find Full Text PDFIodine-promoted direct diamination of α,β-unsaturated ketone to form two C-N bonds has been developed starting from chalcone and secondary amine. This reaction was performed in THF at 50 °C in the presence of I and K CO The protocol is metal-free, operationally simple and carried out under mild conditions, providing an effective new way for directing diamination reactions.
View Article and Find Full Text PDFAn efficient method for the enantioselective construction of tertiary 1,3-diols via Pd-catalyzed asymmetric allylic cycloaddition of vinyloxetanes with an abundant feedstock, formaldehyde, is developed. Using the palladium complex generated in situ from Pd(dba)·CHCl and phosphoramidite L3 as a catalyst under mild conditions, the process allows one to convert racemic 2-substituted 2-vinyloxetanes (1) to the corresponding 1,3-dioxanes (2) as methylene acetal protected tertiary 1,3-diols in high yields with good to excellent enantioselectivities.
View Article and Find Full Text PDFSince there were a few articles to report the treatment of severe pulmonary vasoconstriction induced by protamine in cardiac surgery, we described the use of epoprostenol to reverse this condition.A total of 5 cases of severe pulmonary vasoconstriction induced by protamine in cardiac surgery were reviewed. The demographic, clinical data and treatment process were obtained.
View Article and Find Full Text PDFChlorophyll fluorescence parameter of F/F, as an important index for evaluating crop yields and biomass, is key to guide crop management. However, the shortage of good hyperspectral data can hinder the accurate assessment of wheat F/F. In this research, the relationships between wheat canopy F/F and in-situ hyperspectral vegetation indexes were explored to develop a strategy for accurate F/F assessment.
View Article and Find Full Text PDFAn efficient method for the construction of furanobenzodihydropyran skeletons has been developed through Pd-catalyzed asymmetric decarboxylative cycloaddition of vinylethylene carbonates with 3-cyanochromones. By using a palladium complex generated in situ from [Pd2(dba)3]·CHCl3 and phosphoramidite L3 as a catalyst under mild reaction conditions, the process afforded furanobenzodihydropyrans bearing vicinal quaternary stereocenters in high yields with good to high enantio- and diastereoselectivities.
View Article and Find Full Text PDFAn efficient method for the enantioselective construction of tertiary C-O bond via asymmetric allylic substitution of racemic vinylethylene carbonates with water and alcohols has been developed. Under the cooperative catalysis system of an in situ generated chiral palladium complex and boron reagent in mild conditions, the process allowed rapid access to valuable tertiary alcohols and ethers in high yields with complete regioselectivities and high enantioselectivities. This protocol represented the first example of direct enantioselective formation of a tertiary C-O bond with water as an oxygen donor.
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