| 摘 要： | Base metal catalyzed regioselective cage B–H functionalization has been achieved. Under the assistance of a bidentate directing group, Cu-catalyzed 4+2] annulation of carboranyl amides with internal alkynes affords unprecedented C,B-substituted carborane-fused-pyridone derivatives, whereas the use of terminal alkynes leads to B–H/C(sp)–H dehydrocoupling products. The isolation and structural identification of a notably stable Cu(Ⅰ) intermediate shed light on the reaction mechanism, which is proposed to involve a Cu(Ⅲ) intermediate.
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