Copper(I)-Mediated Direct C–H Functionalization of Carborane Anion: One-Pot Installation of Amino, Hydroxyl, Carbon, and Other Heteroatom Functional Groups at the C1 Vertex

Herein we present the first one-pot C–H amination of the monocarba-closo-dodecaborate anion (1) via deprotonative cupration of the C–H bond of 1 to afford the Cu(I)-ate complex 1-Cu-CB11H11– (1a), followed by oxidation with hydroxylamine derivatives (RONH2). DFT calculation indicated that oxidative addition of the O–N bond to the carboranyl copper(I) species is the key step for introduction of the amino group, and this unique redox characteristic of copper also enables the one-pot installation of various substituents at the C vertex, including hydroxyl, cyano, aryl, alkynyl, chalcogen, and diazene groups, thereby providing the basic architecture for carborane anion-based functionalized materials and pharmaceuticals.