Achieving over 90% Faradaic Efficiency in Cyclohexanone Oxime Electrosynthesis Using the Cu-Mo Dual-Site Catalyst.

Coupling with the nitrate electroreduction reaction (NitRR), the electrosynthesis of cyclohexanone oxime (CHO, the vital feedstock in the nylon-6 industry) from cyclohexanone provides a promising alternative to the traditional energy consumption process. However, it still suffers from low efficiency because selective production of *NH2OH intermediate from NitRR under large current densities is challenging. We here report a Cu1MoOx/nitrogen-doped carbon (NC) electrocatalyst with high-density Cu-Mo dual sites for NitRR to selectively produce and stabilize *NH2OH, with the subsequent cyclohexanone oximation achieving the highest CHO Faradaic efficiency of 94.5% and a yield rate of 3.0 mol g-1 h-1 at an industrially relevant current density of 0.5 A cm-2. Furthermore, in situ characterizations evidenced that the Cu-Mo dual sites in Cu1MoOx/NC effectively inhibited hydrodeoxygenation of hydroxyl-containing intermediates of NitRR, selectively producing *NH2OH and thus achieving cyclohexanone oximation with high efficiency. This work provides a high-performance catalyst for CHO electrosynthesis from nitrogenous waste, showing promising application potential in industrial production of CHO.

Electrochemically Direct Fluorination Functionalization of Styrenes with Different Fluorine Source: Access to Fluoroalkyl Derivatives.

A mild protocol for electrochemically oxidative fluorodifunctionalization of styrenes has been demonstrated. The reaction proceeds under metal, external oxidant, and catalyst free conditions, allowing tunable access to a wide variety of synthetically useful fluoroalkyl derivatives, such as ß-fluorosulfone/fluoromethyl, fluorothiocyanation, and vinylsulfonyl derivatives. Moreover, CsF was shown to be the proper fluorine source for this electrochemical fluorodifunctionalization transformation.

Electrochemical Fluorination Functionalization of gem-Difluoroalkenes with CsF as a Fluorine Source: Access to Fluoroalkyl Building Blocks.

Using easily handled CsF as a fluorine source, an electrochemically metal-free protocol for chemo- and regioselective synthesis of various types of long-chain perfluoroalkyl aromatics with gem-difluoroalkene as a substrate and an alcohol or azole as an additional nucleophile was developed. The eletrochemical transformation could tolerate several functional groups, such as halogens, cyanos, benzyls, and heterocycles, and is amenable to gram-scale. The application of this electrochemical method in radiofluorination was also tested.

Electrochemical Difunctionalization of gem-Difluoroalkenes: A Metal-Free Synthesis of α-Difluoro(alkoxyl/azolated) Methylated Ethers.

A scalable electrochemical difunctionalization of gem-difluoroalkenes to structurally versatile difluoro motifs was achieved. This methodology features reagent-free conditions, good functional group tolerance, and a relatively broad substrate scope. Meanwhile, the electrolysis protocol is easy to handle, and the products show good regio- and chemoselectivity. The reaction mechanism was also preliminarily studied.