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An efficient and broadly applicable rhodium-catalyzed direct ortho-arylation of anilines with aryl iodides relying on readily available aminophosphines as traceless directing groups is reported. Its scope and functional group compatibility were both found to be quite broad as a large variety of both aminophosphines and (hetero)aryl iodides, including complex ones, could be utilized. The ortho-arylated anilines could be obtained in high average yields, without any competing diarylation and with full regioselectivity, which constitutes a major step forward compared to other processes. The reaction is moreover not limited to aryl iodides, as an aryl bromide and a triflate could be successfully used, and could be extended to diarylation. Mechanistic studies revealed the key and unique role of the aminophosphine, acting not only as a substrate but also as a ligand for the rhodium catalyst.
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The direct functionalization of C-H bonds is among the most fundamental chemical transformations in organic synthesis. However, when the innate reactivity of the substrate cannot be utilized for the functionalization of a given single C-H bond, this selective C-H bond functionalization mostly relies on the use of directing groups that allow bringing the catalyst in close proximity to the C-H bond to be activated and these directing groups need to be installed before and cleaved after the transformation, which involves two additional undesired synthetic operations. These additional steps dramatically reduce the overall impact and the attractiveness of C-H bond functionalization techniques since classical approaches based on substrate pre-functionalization are sometimes still more straightforward and appealing. During the past decade, a different approach involving both the inâ situ installation and removal of the directing group, which can then often be used in a catalytic manner, has emerged: the transient directing group strategy. In addition to its innovative character, this strategy has brought C-H bond functionalization to an unprecedented level of usefulness and has enabled the development of remarkably efficient processes for the direct and selective introduction of functional groups onto both aromatic and aliphatic substrates. The processes unlocked by the development of these transient directing groups will be comprehensively overviewed in this review article.
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Metamaterials made of nanoscale inclusions or artificial unit cells exhibit exotic optical properties that do not exist in natural materials. Promising applications, such as super-resolution imaging, cloaking, hyperbolic propagation, and ultrafast phase velocities have been demonstrated based on mostly micrometer-scale metamaterials and few nanoscale metamaterials. To date, most metamaterials are created using costly and tedious fabrication techniques with limited paths toward reliable large-scale fabrication. In this work, we demonstrate the one-step direct growth of self-assembled epitaxial metal-oxide nanocomposites as a drastically different approach to fabricating large-area nanostructured metamaterials. Using pulsed laser deposition, we fabricated nanocomposite films with vertically aligned gold (Au) nanopillars (â¼20 nm in diameter) embedded in various oxide matrices with high epitaxial quality. Strong, broad absorption features in the measured absorbance spectrum are clear signatures of plasmon resonances of Au nanopillars. By tuning their densities on selected substrates, anisotropic optical properties are demonstrated via angular dependent and polarization resolved reflectivity measurements and reproduced by full-wave simulations and effective medium theory. Our model predicts exotic properties, such as zero permittivity responses and topological transitions. Our studies suggest that these self-assembled metal-oxide nanostructures provide an exciting new material platform to control and enhance optical response at nanometer scales.
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Glacier mice are peculiar rolling or stationary moss balls found on the surface of some glaciers. They may harbour an ecological habitat for cold-adapted invertebrates and microorganisms, but little is known about their potential to accumulate and disseminate harmful elements and substances. In this study, we investigate the presence of fallout radionuclides (137Cs, 238Pu, 239Pu, 240Pu, 210Pb) and heavy metals (Pb, As, Hg, Cd) in glacier mice and compare the results to bryophytes from adjacent glacier ecosystems. Samples were collected at Austerdalsbreen, a Norwegian outlet glacier from Jostedalsbreen ice cap. Maximum activity concentrations for bryophytes are 552 ± 12 Bq kg-1 for 137Cs, 3485 ± 138 Bq kg-1 for 210Pb, 0.0223 ± 0.065 Bq kg-1 for 238Pu and 4.34 ± 0.43 Bq kg-1 for 239+240Pu while maximum heavy metals concentrations are 70.5 mg kg-1 for Pb, 1.0 mg kg-1 for As, 1.6 mg kg-1 for Hg and 0.13 mg kg-1 for Cd. Maximum activity concentrations in cryconite are 1973.4 ± 5.0 Bq kg-1 for 137Cs, 3632 ± 593 Bq kg-1 for 210Pb, 0.51 ± 0.11 Bq kg-1 for 238Pu and 13.1 ± 1.4 Bq kg-1 for 239+240Pu and maximum heavy metal concentrations are 50.4 mg kg-1 for Pb, 3.4 mg kg-1 for As, 1.5 mg kg-1 for Hg and 0.082 mg kg-1 for Cd. We find that glacier mice show lower activity concentrations of radionuclides compared to cryoconite. The major source of plutonium isotopes is related to global fallout, whereas detected radio-cesium may be additionally affected by post-Chernobyl fallout to an unknown extent. Comparison between glacier surface and adjacent glacial habitats shows higher concentrations of heavy metals in glacier mice on the glacier ice surface and medial moraines compared to bryophytes in the glacier forefield. Glacier mice exported from a receding glacier may affect the cycling of radioactive and metal pollutants in developing proglacial ecosystems.
Asunto(s)
Cubierta de Hielo , Metales Pesados , Metales Pesados/análisis , Noruega , Cubierta de Hielo/química , Animales , Monitoreo del Ambiente , Ceniza Radiactiva/análisis , Briófitas/química , Radioisótopos , Radioisótopos de Cesio/análisisRESUMEN
Ammonium salts are usually considered as highly challenging to reduce into the corresponding radicals because of the strength of their carbon-nitrogen bond. Here, we disclose that several ammonium salts can be readily activated using iridium photoredox catalysis to form radicals and illustrate the synthetic utility of this activation of strong C-N bonds with hydrodeamination reactions and radical couplings. Cyclic voltammetry was exploited to rationalize the reactivity observed for the activation of these ammonium salts.
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An original and straightforward entry to polysubstituted indenes from readily available ynamides is reported. Upon reaction with a N-heterocyclic carbene-gold complex under mild conditions, activated keteniminium ions are generated whose unique electrophilicity triggers a [1,5]-hydride shift and a subsequent cyclization. The presence of an endocyclic enamide in the densely functionalized resulting indenes was shown to be especially useful and versatile, offering a range of opportunities for their further postfunctionalization.
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A general anti-Baldwin radical 4-exo-dig cyclization from nitrogen-substituted alkynes is reported. Upon reaction with a heteroleptic copper complex in the presence of an amine and under visible light irradiation, a range of ynamides were shown to smoothly cyclize to the corresponding azetidines, useful building blocks in natural product synthesis and medicinal chemistry, with full control of the regioselectivity of the cyclization resulting from a unique and underrated radical 4-exo-dig pathway.
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Li2MnO3 is an attractive cathode material due to its low cost, nontoxicity and potentially high capacity. However, its electrochemical inactivity, its poor electronic conductivity, and uncertainty about its underlying mechanism have limited its development. In this work, an in situ technique for extraction of Li and O during deposition of the thin film cathode is developed to investigate structural and electrochemical effects in a controlled fashion. MnO2 has been observed in samples with severe O and Li deficiency (capacity of 115 mAh g(-1)), while Li2MnO3 cathodes with slight excess of O and Li (capacity of 225 mAh g(-1)) can be synthesized by tuning growth conditions appropriately. Formation of a MnO2 phase, especially in Li and O deficient structures, could be a possible reason for irreversible capacity loss in Li2MnO3 related materials. Further investigation into stoichiometric and microstructure variations enabled by this technique allows rapid investigation of Li2MnO3 as well as other Li-rich composites.