Copper catalyzed/mediated direct B–H alkenylation/alkynylation in carboranes  

作　　者：Yu Chen Yik Ki Au Yangjian Quan Zuowei Xie 

机构地区：[1]Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong

出　　处：《Science China Chemistry》2019年第1期74-79,共6页中国科学（化学英文版）

基　　金：supported by the Research Grants Council of The Hong Kong Special Administration Region(14304115,14305017);CUHK Direct Grant and Incentive Grant from Faculty of Science,CUHK

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.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.

关 键 词：[4+2] annulation ALKYNYLATION B-H activation base metal catalysis CARBORANE 

分 类 号：O621.251[理学—有机化学]