Distinct selectivity control in Cp*Co III -catalyzed domino C−H activation/pyridine directing group migration/ alkyne annulation has been accomplished through the nucleophilicity of an organometallic cobalt intermediate with a d 6 electron configuration. Detailed mechanistic studies provided compelling evidence for a facile C−H activation along with a favorable migration of the directing group for the Cp*Co III catalysis, rather than the β-oxygen elimination observed for a (CO) 3 Mn I manifold.

Electrocatalyzed oxidative B À H nitrogenations of nido-carborane (nido-7,8-C 2 B 9 H 12 À) with N-heterocycles have been established, enabling the preparation of various Nsubstituted 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 userfriendly access to novel amino acid and fluorogenic borondipyrrin (BODIPY)-labeled nido-carborane hybrids.

B–H: site-selective B(3,4)–H arylations were accomplished at room temperature by versatile palladium catalysis enabled by weakly coordinating amides.

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...

Carboranes are boron-carbon molecular clusters that possess unique properties, such as their icosahedron geometry, high boron content, and delocalized three-dimensional aromaticity. These features render carboranes valuable building blocks for applications in supramolecular design, nanomaterials, optoelectronics, organometallic coordination chemistry, and as boron neutron capture therapy (BNCT) agents. Despite tremendous progress in this field, stoichiometric chemical redox reagents are largely required for the oxidative activation of carborane cages. In this context, electrosyntheses represent an alternative strategy for more sustainable molecular syntheses. It is only in recent few years that considerable progress has been made in electrochemical cage functionalization of carboranes, which are summarized in this Minireview. We anticipate that electrocatalysis will serve as an increasingly powerful stimulus within the current renaissance of carborane electrochemistry.