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The direct electrochemical carboxylation of aryl, benzyl and alkyl halides by CO is described using a magnesium anode and a nickel foam cathode in an undivided cell. The process employs a sacrificial anode and does not require the additional use of a transition metal catalyst or demanding conditions, as the reactions are carried out under galvanostatic mode, at -10 °C and with commercial DMF. Under these operationally simple conditions, an important range of carboxylic acids are affordable.

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Enantioselective reductive cross-couplings to forge C(sp)-C(sp) bonds by merging electrochemistry with nickel catalysis.

Nat Commun

January 2025

State Key Laboratory of Organometallic Chemistry, Shanghai of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, PR China.

Motivated by the inherent benefits of synergistically combining electrochemical methodologies with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling of benzyl chlorides with aryl halides, yielding chiral 1,1-diaryl compounds with good to excellent enantioselectivity. This catalytic reaction can not only be applied to aryl chlorides/bromides, which are challenging to access by other means, but also to benzyl chlorides containing silicon groups. Additionally, the absence of a sacrificial anode lays a foundation for scalability.

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Electrocatalytic dehalogenative deuteration is a sustainable method for precise deuteration, whereas its Faradaic efficiency (FE) is limited by a high overpotential and severe D evolution reaction (DER). Here, Cu site-adjusted adsorption and crown ether-reconfigured interfacial DO are reported to cooperatively increase the FE of dehalogenative deuteration up to 84% at -100 mA cm. Cu sites strengthen the adsorption of aryl iodides, promoting interfacial mass transfer and thus accelerating the kinetics toward dehalogenative deuteration.

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An efficient Suzuki cross-coupling reaction under continuous flow conditions was developed utilizing an immobilized solid supported catalyst consisting of bimetallic nickel-palladium nanoparticles (Ni-Pd/MWCNTs). In this process, the reactants can be continuously pumped into a catalyst bed at a high flow rate of 0.6 mL/min and the temperature of 130 °C while the Suzuki products are recovered in high steady-state yields for prolonged continuous processing.

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Palladium nanoparticles were supported on L-H-functionalized KIT-6 (KIT-6@L-H-Pd) and evaluated using various characterization techniques such as TGA, FT-IR, SEM, XRD, EDS, and BET. KIT-6@L-H-Pd showed excellent catalytic performance as a recyclable nanocatalyst for the oxidation of sulfides to sulfoxides and the amination of aryl halides. This approach offers multiple benefits, including the use of readily available and cost-effective materials, a straightforward procedure, short reaction durations, high yields, and a catalyst that is easy to separate and reuse.

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