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Vicinal diamines are a common structural motif in bioactive natural products, therapeutic agents, and molecular catalysts, motivating the continuing development of efficient, selective, and sustainable technologies for their preparation. We report an operationally simple and environmentally friendly protocol that converts alkenes and sodium azide—both readily available feedstocks—to 1,2-diazides. Powered by electricity and catalyzed by Earth-abundant manganese, this transformation proceeds under mild conditions and exhibits exceptional substrate generality and functional group compatibility. Using standard protocols, the resultant 1,2-diazides can be smoothly reduced to vicinal diamines in a single step, with high chemoselectivity. Mechanistic studies are consistent with metal-mediated azidyl radical transfer as the predominant pathway, enabling dual carbon-nitrogen bond formation.

The heterodifunctionalization of alkenes is an efficient and straightforward method for the preparation of highly functionalized molecules. However, enantioselective introduction of two different carbon-based functional groups in a single step using readily accessible and inexpensive starting materials presents a significant challenge. Herein, we report an electrochemical copper-catalyzed protocol for the asymmetric cyanoesterification of vinylarenes using commercially available alkyl carbazates and trimethylsilyl cyanide (TMSCN) as the sources of ester and cyano groups, respectively. The desired products could be obtained with good yields and enantioselectivities under mild conditions without the need for stoichiometric oxidants, providing sustainable access to versatile synthetic intermediates that could be smoothly converted into a variety of useful chiral building blocks. Mechanistic data are consistent with electrochemical copper-catalyzed generation of alkoxycarbonyl radicals from alkyl carbazates and the copper catalyst is also responsible for the stereoselective C–CN bond formation. The potential synthetic utility of this new electrocatalytic protocol is demonstrated in the concise synthesis of pharmacologically active molecules. Enantioselective introduction of two different carbon-based functional groups in a single step using readily accessible and inexpensive starting materials presents a significant challenge. Here the authors report an electrochemical copper-catalyzed protocol for the asymmetric cyanoesterification of vinylarenes using commercially available alkyl carbazates and trimethylsilyl cyanide (TMSCN) as the sources of ester and cyano groups, respectively.

The development of robust, practical, and chemoselective methods for introducing the difluoromethyl (CF₂H) group into organic molecules is highly sought after in the fields of pharmaceutical and agrochemical design. Herein, we report a Fe/Ni dual-transition-metal electrocatalytic strategy for difluoromethylation of (hetero)aryl halides, using difluoroacetate—the most abundant source of the CF₂H group—as an effective difluoromethylating reagent. A diverse array of aryl and heteroaryl halides, bearing synthetically useful functional groups, can be readily converted into the corresponding difluoromethylated products with good efficiency. This difluoromethylation protocol is readily scalable and is successfully applied to the preparation and late-stage functionalization of bioactive molecules. The development of robust, practical, and chemoselective methods for introducing the difluoromethyl (CF₂H) group into organic molecules is highly sought after in the fields of pharmaceutical and agrochemical design. Herein, the authors report a Fe/Ni dual-transition-metal electrocatalytic strategy for difluoromethylation of (hetero)aryl halides, using difluoroacetate — the most abundant source of the CF₂H group — as an effective difluoromethylating reagent.

Chiral nitriles and their derivatives are prevalent in pharmaceuticals and bioactive compounds. Enantioselective alkene hydrocyanation represents a convenient and efficient approach for synthesizing these molecules. However, a generally applicable method featuring a broad substrate scope and high functional group tolerance remains elusive. Here, we address this long-standing synthetic problem using dual electrocatalysis. Using this strategy, we leverage electrochemistry to seamlessly combine two canonical radical reactions—cobalt-mediated hydrogen-atom transfer and copper-promoted radical cyanation—to accomplish highly enantioselective hydrocyanation without the need for stoichiometric oxidants. We also harness electrochemistry’s unique feature of precise potential control to optimize the chemoselectivity of challenging substrates. Computational analysis uncovers the origin of enantio-induction, for which the chiral catalyst imparts a combination of attractive and repulsive non-covalent interactions to direct the enantio-determining C–CN bond formation. This work demonstrates the power of electrochemistry in accessing new chemical space and providing solutions to pertinent challenges in synthetic chemistry.A general method for the enantioselective hydrocyanation of alkenes has been a long-standing synthetic challenge. Now, using a dual electrocatalytic approach that combines two synergistic redox catalytic cycles, a wide variety of chiral nitriles can be synthesized from conjugated alkenes in high enantioselectivity.

This protocol describes an electrochemical synthesis of 1,2-diazides from alkenes. Organic azides are highly versatile intermediates for synthetic chemistry, materials, and biological applications. 1,2-Diazides are commonly reduced to form 1,2-diamines, which are prevalent structural motifs in bioactive natural products, therapeutic agents, and molecular catalysts. The electrochemical formation of 1,2-diazides involves the anodic generation of an azidyl radical from sodium azide, followed by two successive additions of this N-centered radical to the alkene, and is assisted by a Mn catalyst. The electrosynthesis of 1,2-diazides can be carried out using various experimental setups comprising custom-made or commercially available reaction vessels and a direct-current power supply. Readily accessible electrode materials can be used, including carbon (made from reticulated vitreous carbon and pencil lead), nickel foam, and platinum foil. This protocol is also demonstrated using ElectraSyn, a standardized electrochemistry kit. Compared with conventional synthetic approaches, electrochemistry allows for the precise control of the anodic potential input, eliminates the need for stoichiometric and often indiscriminate oxidants, and minimizes the generation of wasteful byproducts. As such, our electrocatalytic synthesis exhibits various advantages over existing methods for alkene diamination, including sustainability, operational simplicity, substrate generality, and exceptional functional-group compatibility. The resultant 1,2-diazides can be smoothly reduced to 1,2-diamines in a single step with high chemoselectivity. To exemplify this, we include a procedure for catalytic hydrogenation using palladium on carbon. This protocol, therefore, constitutes a general approach to accessing 1,2-diazides and 1,2-diamines from alkenes.

We report a practical and sustainable electrophotochemical metal-catalyzed protocol for decarboxylative cyanation of simple aliphatic carboxylic acids. This environmentally friendly method features easy availability of substrates, broad functional group compatibility, and directly converts a diverse range of aliphatic carboxylic acids including primary and tertiary alkyl acids into synthetically versatile alkylnitriles without using chemical oxidants or costly cyanating reagents under mild reaction conditions.