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Samarium diiodide (SmI2) mediated reductive coupling reactions are powerful methods for the construction of carbon-carbon bond in organic synthesis. Despite the extensive development in recent decades, successful examples of the corresponding asymmetric reactions remained scarce, probably due to the involvement of highly reactive radical intermediates. In this Article, we report an enantioselective dearomatization of indoles via SmI2-mediated intermolecular reductive coupling with ketones. The utilization of samarium reductant supported by chiral tridentate aminodiol ligands allows the facile synthesis of indoline molecules bearing two contiguous stereogenic centers in high yields (up to 99%) and stereoselectivity (up to 99:1 er and >20:1 dr). Combined experimental and computational investigations suggested that parallel single-electron transfer to each substrate from the chiral samarium reductant allows the radical-radical recombination in an enantioselective manner, which is a unique mechanistic scenario in SmI2-mediated reductive coupling reactions.
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Herein, an Ir-catalyzed asymmetric allylic substitution reaction of methyl azaarenes is described. Azaarenes such as (benzo)thiazole, oxazole, benzoimidazole, pyridine, and (iso)quinoline are all tolerated. The corresponding chiral azaarene derivatives are obtained in good yields with high enantioselectivity (up to 96 % yield and 99 % ee). The utilization of the Knochel reagent TMPZnBrâ LiBr warrants the in situ formation of benzylic nucleophiles without additional activating reagents. 1 Hâ NMR studies suggested a two-fold function of the Knochel reagent in this reaction. The synthetic utility of this method has been showcased by a concise enantioselective synthesis of an allosteric protein kinase modulator.
Assuntos
Irídio , Catálise , Irídio/química , EstereoisomerismoRESUMO
Spirocyclic hexadienones with multiple stereogenic centers are frequently found in natural products but remain challenging targets to synthesize. Herein, we report the enantioselective desymmetrization of bisphenol derivatives via Ir-catalyzed allylic dearomatization reactions, affording spirocyclic hexadienone derivatives with up to three contiguous stereogenic centers in good yields (up to 90%) and excellent enantioselectivity (up to 99% ee). The high efficiency of this reaction is exemplified by the short reaction time (30 min), low catalyst loading (down to 0.2 mol %), and ability to perform the reaction on a gram-scale. The total syntheses of (+)-tatanan B and (+)-tatanan C were also realized using this Ir-catalyzed allylic dearomatization reaction as a key step.
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The stereodivergent iridium-catalyzed allylic alkylation and fluorination of acyclic ketones is described. α-Pyridyl-α-fluoroketones with vicinal tertiary and quaternary stereocenters were obtained in moderate to excellent yields and stereoselectivities. Distinct from known stereodivergent synthesis, for which two different chiral catalysts are required in general, herein we report a sequence-dependent stereodivergent synthesis. With only a single chiral Ir catalyst, all four possible stereoisomers of the products were prepared from the same starting materials by simply adjusting the sequence of asymmetric allylic alkylation and fluorination and varying the absolute configuration of the Ir catalyst.
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Ketones and aldehydes are employed as enol O-nucleophiles in an iridium-catalyzed asymmetric allylic substitution reaction. The reaction proceeds well in the presence of a well-defined chiral iridium complex under mild conditions. A series of chiral 2 H-1,4-oxazine skeletons can be obtained in up to 94% yield with 99% ee. The utility of this novel method has been demonstrated by its implementation in the first enantioselective synthesis of (+)-chelonin A.
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Objective: A model of chronic infectious mandibular defect (IMD) caused by mixed infection with Staphylococcus aureus and Pseudomonas aeruginosa was established to explore the occurrence and development of IMD and identify key genes by transcriptome sequencing and bioinformatics analysis. Methods: S. aureus and P. aeruginosa were diluted to 3 × 108 CFU/mL, and 6 × 3 × 3 mm defects lateral to the Mandibular Symphysis were induced in 28 New Zealand rabbits. Sodium Morrhuate (0.5%) and 50 µL bacterial solution were injected in turn. The modeling was completed after the bone wax closed; the effects were evaluated through postoperative observations, imaging and histological analyses. Gene Ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway, and proteinâprotein interaction (PPI) network analyses were performed to investigate the function of the differentially expressed genes (DEGs). Results: All rabbits showed characteristics of infection. The bacterial cultures were positive, and polymerase chain reaction (PCR) was used to identify S. aureus and P. aeruginosa. Cone beam CT and histological analyses showed inflammatory cell infiltration, pus formation in the medullary cavity, increased osteoclast activity in the defect area, and blurring at the edge of the bone defect. Bioinformatics analysis showed 1,804 DEGs, 743 were upregulated and 1,061 were downregulated. GO and KEGG analyses showed that the DEGs were enriched in immunity and osteogenesis inhibition, and the core genes identified by the PPI network were enriched in the Hedgehog pathway, which plays a role in inflammation and tissue repair; the MEF2 transcription factor family was predicted by IRegulon. Conclusion: By direct injection of bacterial solution into the rabbit mandible defect area, the rabbit chronic IMD model was successfully established. Based on the bioinformatics analysis, we speculate that the Hedgehog pathway and the MEF2 transcription factor family may be potential intervention targets for repairing IMD.
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Asymmetric ring-opening of 7-oxabenzonorbornadienes is achieved via Co-catalyzed indole C-H functionalization. The utilization of chiral Co-catalyst consisting of a binaphthyl-derived trisubstituted cyclopentadienyl ligand resulted in high yields (up to 99%) and excellent enantioselectivity (>99% ee) for the target products with tolerance for diverse functional groups. Opposite diastereoselectivities are obtained with chiral Co-catalyst or Cp*CoI2CO. Combined experimental and computational studies suggest ß-oxygen elimination being the selectivity-determining step of the reaction. Meanwhile, the reactions of 7-azabenzonorbornadiene could also be executed in a diastereodivergent manner.
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BACKGROUND: Morphological anomalies of teeth, including talon cusp, dens evaginatus, gemination, fusion, concrescence, root dilaceration, and taurodontism, always involve changes in the enamel, cementum and dentin. Diagnosing concrescent teeth through routine clinical examination alone is difficult, and most cases of concrescence are found accidentally during extraction. A definite preoperative diagnosis of concrescence would contribute to a better treatment plan and fewer undesirable complications. CASE SUMMARY: A 47-year-old woman who complained of left maxillary first molar loss for half a year presented to our department seeking treatment by dental implant restoration. Panoramic radiography and cone-beam computed tomography (CBCT) showed an unclear boundary between the distal root of the second molar and the mesial root of the third molar. The teeth were extracted under local anesthesia, and a definite diagnosis of concrescence was made by histopathological examination. CONCLUSION: CBCT is a useful tool for diagnosing and planning the management of tooth concrescence and may be beneficial for reducing unnecessary complications.
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OBJECTIVE: To evaluate the effect of sandblasting or acid etching on the three-point bending strength to the modified polyetheretherketone (PEEK). METHODS: Forty-eight bars (15 mm×2 mm×1 mm) of specimens were fabricated from the modified PEEK (BioHPP). They were randomly divided into the following groups: A, B, C and D groups, which were blasted with alumina particles; E, F, and G groups, which were etched with 98% concentrated sulfuric acid; and control group H. The sand blast pressure of groups A, B and C was 0.2 MPa, and the grain sizes of the sand blasted were 120, 50, and 250 µm, respectively. Group D was blasted with 120 µm particle size at 0.7 MPa pressure. Groups E, F and G were acid etched for 60, 120, and 300 s, respectively. No surface treatment was conducted in group H. After all the specimens were processed, one sample was randomly selected from each group to observe its surface morphology under a scanning electron microscope (SEM), and the other specimens were tested for their three-point bending strength. SPSS 22.0 software was used to analyze the experimental data and to test whether the difference was statistically significant. RESULTS: SEM observation showed that the surface morphology of the specimen changed after the treatment and revealed different degrees of cracks, pits, or voids. The three-point bending test indicated that the strength of the specimens treated with sandblasting or concentrated sulfuric acid decreased compared with that of the control group (P<0.05). At the same pressure, no significant difference in flexural strength was observed among groups A, B, and C (P>0.05). The strength of group D was lower than that of group A at the same particle size (P<0.05), and no significant difference was found in the bending strength of the specimens etched with concentrated sulfuric acid (P>0.05). CONCLUSIONS: The bending strength of BioHPP could be significantly decreased by surface sand blasting or concentrated sulfate etching as the sandblasting pressure increased, but the bending strength did not decrease as sand particle size and acid etching time changed.
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Colagem Dentária , Cimentos de Resina , Benzofenonas , Cetonas , Teste de Materiais , Microscopia Eletrônica de Varredura , Polietilenoglicóis , Polímeros , Resistência ao Cisalhamento , Propriedades de SuperfícieRESUMO
OBJECTIVE: This study aims to assess the effects of the different thicknesses of body-shade resin layers on the color of polyetheretherketone (PEEK)-Crea.lign restorations. METHODS: Five PEEK specimens with the thickness of 0.6 mm were prepared. The color values of PEEK specimens were measured. Afterward, opaque-shade resin layers (0.1 mm) and body-shade resin layers (1.5 mm) were stacked with mold. The five specimens were evenly ground to a thickness of 1.4, 1.2, 1.0, 0.8, 0.6, 0.4, 0.2, and 0.0 mm in sequence. After grinding and ultrasonic cleaning, the color value was measured. RESULTS: With the constant thickness of PEEK and 0.1 mm thickness of opaque-shade resin layer, the L*, a*, and b* values all showed downward trend with the increased thickness of the body-shade resin layer (1.0-1.4 mm). With the constant thickness of PEEK and 0.1 mm thickness of opaque-shade resin layer, the color difference between the adjacent groups was less than 1.5 NBS. This difference between nonadjacent groups was more than 1.5 NBS when the thickness of the body-shade resin layer reached 0.6 mm. Color difference between PEEK-Crea.lign restoration and PEEK was more than 1.5 NBS. CONCLUSIONS: The thickness change in the body-shade resin layers influence the color of the PEEK-Crea.lign restorations. Using A2 shade Crea.lign, opaque-shade resin layer thickness is 0.1 and 0.6 mm thickness of body-shade resin layer can produce color which clinically acceptable.
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Cor , Resinas Compostas , Cetonas , Benzofenonas , Polietilenoglicóis , PolímerosRESUMO
OBJECTIVE: To discuss the influence of nano-silica content which was hydrolyzed by tetraethyl orthosioate (TEOS) on the aluminum borate whisker (AlBw) and silica filler composite resins on flexural properties. METHODS: The nanometer-size silicon dioxide (SiO2) particles were prepared by sol-gel method based on tetraethyl orthosioate. Different proportion of AlBw and SiO2 were fused and attached onto the surface of AlBw through high temperature, then polymerized with resin matrix after surface siliconization and their flexural strength and flexural modulus were determined. The effects of heat treatment to the surface morphology of AlBw and the shapes of the mixture at various proportions were characterized by TEM. RESULTS: The flexural properties of dental composite resins with AlBw-SiO2 compound as inorganic fillers were significantly improved. The flexural property of a new type of dental composite resins was(130.29 +/- 8.38) MPa, when the mass ratio of AlBw and nano-SiO2 particle was 3:1. CONCLUSION: Nano-silica content which was hydrolyzed by tetraethyl orthosioate improved flexural properties of the aluminum borate whisker and silica filler composite resins.
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Boratos , Dióxido de Silício , Resinas Acrílicas , Alumínio , Animais , Resinas Compostas , Teste de Materiais , Maleabilidade , Poliuretanos , Silanos , VibrissasRESUMO
OBJECTIVE: To compare the fracture resistances of pulpless teeth restored with FRC (Fiber Reinforced Composite) posts and three kinds of resin core material. METHODS: A total of 42 recently extracted upper incisors were randomly divided into 3 groups. Group A was restored with prefabricated glass-fiber posts and Artglass polymer core; group B with prefabricated glass-fiber posts and Charisma composite resin core; and group C with prefabricated glass-fiber posts and AB composite resin core. In every group, the core material was processed by hot-press and non hot-press respectively. The posts size and shape were identical in the 3 groups. All teeth were fully covered with polycarbonate resin crowns. Fracture resistance was measured by applying point force at 130 degrees to the long axis of the teeth on an universal testing machine. RESULTS: Mean fracture threshold was 505.4 N +/- 42.0 N and 564.1 N +/- 41.7 N in group A, 411.3 N +/- 23.3 N and 315.3 N +/- 19.1 N in group B and 358.4 N +/- 36.1 N and 423.4 N +/- 47.5 N in group C. In all groups, there was no posts fracture and polycarbonate resin crowns fragmentation. CONCLUSION: The composite restoration of FRC posts combined with resin core and resin crown can improve the fracture resistance of the pulpless roots. The strength of resin core material can be increased by hot-press methods.