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The reaction of organometallic reagents, e.g. alkyllithiums, cuprates and alkylcoppers, with α-haloimines gave selectively a variety of synthetically useful reactions, including coupling to 1,4-diimines, homologation, and production of heterocycles.  相似文献   
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α-Chloroaldimines are arylated at the α-position under Friedel-Crafts conditions via intermediacy of α-imidoylcarbenium ions.  相似文献   
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Ruthenium nanocatalysis can provide effective deuteration and tritiation of oxazole, imidazole, triazole and carbazole substructures in complex molecules using D2 or T2 gas as isotopic sources. Depending on the substructure considered, this approach does not only represent a significant step forward in practice, with notably higher isotope uptakes, a broader substrate scope and a higher solvent applicability compared to existing procedures, but also the unique way to label important heterocycles using hydrogen isotope exchange. In terms of applications, the high incorporation of deuterium atoms, allows the synthesis of internal standards for LC-MS quantification. Moreover, the efficacy of the catalyst permits, even under subatmospheric pressure of T2 gas, the preparation of complex radiolabeled drugs owning high molar activities. From a fundamental point of view, a detailed DFT-based mechanistic study identifying undisclosed key intermediates, allowed a deeper understanding of C−H (and N−H) activation processes occurring at the surface of metallic nanoclusters.  相似文献   
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We propose a straightforward access to a rotating light-emitting device powered by wireless electrochemistry. A magnetic stirrer is used to rotate a light-emitting diode (LED) due to the intrinsic magnetic properties of the tips that contain iron. At the same time, the LED is submitted to an electric field and acts as a bipolar electrode. The electrochemical processes that are coupled on both extremities of the LED drive an electron flow across the device, resulting in light emission. The variation of the LED alignment in time enables an alternating light emission that is directly controlled by the rotation rate. The stirring also enables a continuous mixing of the electrolyte that improves the stability of the output signal. Finally, the LED brightness can readily reveal a change of chemical composition in the electrolyte solution.  相似文献   
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Miniaturized autonomous chemo‐electronic swimmers, based on the coupling of spontaneous oxidation and reduction reactions at the two poles of light‐emitting diodes (LEDs), are presented as chemotactic and magnetotactic devices. In homogeneous aqueous media, random motion caused by a bubble‐induced propulsion mechanism is observed. However, in an inhomogeneous environment, the self‐propelled devices exhibit positive chemotactic behavior, propelling themselves along a pH or ionic strength gradient (?pH and ?I, respectively) in order to reach a thermodynamically higher active state. In addition, the intrinsic permanent magnetic moment of the LED allows self‐orientation in the terrestrial magnetic field or following other external magnetic perturbations, which enables a directional motion control coupled with light emission. The interplay between chemotaxis and magnetotaxis allows fine‐tuning of the dynamic behavior of these swimmers.  相似文献   
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