Anthranil: An Aminating Reagent Leading to Bifunctionality for Both C(sp(3) )-H and C(sp(2) )-H under Rhodium(III) Catalysis

Songjie Yu; Guodong Tang; Yingzi Li; Xukai Zhou; Yu Lan; Xingwei Li

doi:10.1002/anie.201602224

Anthranil: An Aminating Reagent Leading to Bifunctionality for Both C(sp(3) )-H and C(sp(2) )-H under Rhodium(III) Catalysis

Angew Chem Int Ed Engl. 2016 Jul 18;55(30):8696-700. doi: 10.1002/anie.201602224. Epub 2016 Apr 28.

Authors

Songjie Yu¹, Guodong Tang¹, Yingzi Li², Xukai Zhou¹, Yu Lan³, Xingwei Li⁴

Affiliations

¹ Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
² School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030, China.
³ School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030, China. lanyu@cqu.edu.cn.
⁴ Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China. xwli@dicp.ac.cn.

PMID: 27121133
DOI: 10.1002/anie.201602224

Abstract

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.

Keywords: C−H activation; amination; arenes; reaction mechanisms; rhodium.

Publication types

Research Support, Non-U.S. Gov't