N-Ligand-Enabled Aromatic Nucleophilic Amination of 1,2-Diaryl-o-Carboranes with (R 2 N) 2 Mg for Selective Synthesis of 4-R 2 N-o-Carboranes and 2-R 2 N-m-Carboranes.

The nucleophilic aromatic BH substitution reaction of carboranes is uncommon, compared to the electrophilic one. This work reported a pyridine-enabled transition-metal-free regioselective nucleophilic aromatic cage B(4)-H amination of 1,2-diaryl-o-carboranes with magnesium bisamides, giving a series of B(4)-aminated o-carboranes. DFT calculations showcased a stepwise B-N formation/B-H cleavage process, in which Mg-H formation/cage closure is the rate-determining step. Unprecedentedly, in the presence of 4,4'-di-tert-butyl-2,2'-dipyridyl (dtbpy), a tandem B(4)-amination/cage isomerization reaction of o-carboranes was discovered for the facile preparation of B(2)-aminated m-carboranes. Control experiments indicated that magnesium complex, bidentate ligand (dtbpy) and reaction temperature were crucial in the cage isomerization process. This direct nucleophilic aromatic cage B-H amination reaction offers an alternative strategy for selective amination of o- and m-carboranes.