Anthranil: An Aminating Reagent Leading to Bifunctionality for Both C(sp(3) )-H and C(sp(2) )-H under Rhodium(III) Catalysis.
Previous direct C-H nitrogenation suffered from simple amidation/amination with limited atom-economy and is mostly limited to C(sp(2) )-H substrates. In this work, anthranil was designed as a novel bifunctional aminating reagent for both C(sp(2) )-H and C(sp(3) )-H bonds under rhodium(III) catalysis, thus affording a nucleophilic aniline tethered to an electrophilic carbonyl. A tridendate rhodium(III) complex has been isolated as the resting state of the catalyst, and DFT studies established the intermediacy of a nitrene species.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Songjie
S
Yu
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Guodong
G
Tang
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030, China.
Yingzi
Y
Li
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Xukai
X
Zhou
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030, China. lanyu@cqu.edu.cn.
Yu
Y
Lan
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. xwli@dicp.ac.cn.
Xingwei
X
Li
C−H activation; amination; arenes; reaction mechanisms; rhodium