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Copper-catalyzed electrochemical direct chalcogenations of o-carboranes was established at room temperature. Thereby, a series of cage C-sulfenylated and C-selenylated o-carboranes anchored with valuable functional groups was accessed with high levels of position- and chemo-selectivity control. The cupraelectrocatalysis provided efficient means to activate otherwise inert cage C–H bonds for the late-stage diversification of o-carboranes., Copper-catalyzed electrochemical cage C–H chalcogenation of o-carboranes has been realized to enable the synthesis of various cage C-sulfenylated and C-selenylated o-carboranes.

Electrocatalyzed oxidative B−H nitrogenations of nido‐carborane (nido‐7,8‐C2B9H12 −) with N‐heterocycles have been established, enabling the preparation of various N‐substituted nido‐carboranes without chemical oxidants or metal catalyst under ambient conditions. The electrolysis manifold occurred with high levels of efficiency as well as chemo‐ and position‐ selectivity, employing sustainable electricity as the sole oxidant. The strategy set the stage for a user‐friendly access to novel amino acid and fluorogenic boron‐dipyrrin (BODIPY)‐labeled nido‐carborane hybrids., Metal‐free electrocatalyzed B−H nitrogenation is used to synthesize various N‐heterocyclic nido‐carboranes.

A ruthenium‐catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes has been established, enabling the preparation of various bridgehead N‐fused [5,6]‐bicyclic heteroarenes through regioselective electrochemical C−H/N−H annulation without chemical metal oxidants. Novel azaruthenabicyclo[3.2.0]heptadienes were fully characterized and identified as key intermediates. Mechanistic studies are suggestive of an oxidatively induced reductive elimination pathway within a ruthenium(II/III) regime., New mechanism: A ruthenium‐catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes delivers bridgehead N‐fused [5,6]‐bicyclic heteroarenes through regioselective C−H/N−H annulation without metal oxidants. Novel azaruthenabicyclo[3.2.0]heptadienes were identified as key intermediates. Mechanistic studies suggest an oxidatively induced reductive elimination pathway within a ruthenium(II/III) regime.

Synthetically meaningful isoindolones were accessed by cupraelectro-catalyzed C–H activation with electricity as terminal oxidant. Thus, a versatile, inexpensive, and nontoxic Cu(OAc)2 catalyst ena...

Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we herein describe the first electrochemical rhodium-catalyzed C-H activation that avoids hazardous chemical oxidants. Environmentally benign twofold C-H/C-H functionalizations were accomplished with weakly coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant and generating H2 as the sole byproduct.