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-<i>closo</i>-dodecaborate anion (<b>1</b>) via deprotonative cupration of the C-H bond of <b>1</b> to afford the Cu(I)-ate complex [1-Cu-CB₁₁H₁₁^-] (<b>1a</b>), 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.