Transition Metal Catalyzed Direct Amination of the Cage B(4)–H Bond in o-Carboranes: Synthesis of Tertiary, Secondary, and Primary o-Carboranyl Amines

• DOI: 10.1021/jacs.6b07086
• Publication Date: 2016-09-14T16:22:16Z
• Authors: Hairong Lyu; Yangjian Quan; Zuowei Xie
• Keywords: Primary (astronomy); Cage

Transition metal catalyzed regioselective amination of the cage B(4)–H bond in o-carboranes has been achieved for first time using O-benzoyl hydroxylamines or organic azides as reagents, leading to preparation a series tertiary and secondary carboranyl amines. Both reactions proceeded under mild conditions without addition any external oxidants. Hydrogenolysis resultant product 4-N(CH2Ph)2-o-carborane afforded primary amine, 4-amino-o-carborane, quantitative yield.