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Copper(I)-Mediated Direct C-H Functionalization of Carborane Anion: One-Pot Installation of Amino, Hydroxyl, Carbon,
Yu Kitazawa1,2, Yuhi Ito1, Kazunori Miyamoto3,2
1Department of Chemistry and Materials, Faculty of Textile Science and Technology, Shinshu University, Ueda, 386-8567, Japan.
Abstract:
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.
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