The first biocompatible iron-catalyzed benzylic C (sp ³ )–H amination of methylarenes with NFSI under ligand and additional oxidant free conditions is described.

An asterisk after the author name Fengyu Bao has been omitted by mistake. The correct version is as follows: Fengyu Bao*aZhikai LiubHaixin BaiaHaiyan ZhangaPengfei Liu*bQidong ZhangcGuobi Chai*ca College of Science, Henan Agricultural University, Zhengzhou 450002, P. R. of China baofengyu@henau.edu.cnb College of Tobacco, Henan Agricultural University, Zhengzhou 450002, P. R. of China liupengfei523@126.comc Zhengzhou Tobacco Research Institute, Zhengzhou 450001, P. R. of China chaigb@ztri.com.cn Synlett 2020, 31, 1501. Publication Date: 09 October 2020 (online) © 2020. Thieme. All rights reserved Georg Thieme Verlag KG Rüdigerstraße 14, 70469 Stuttgart, Germany

Dedicated to Ms. Gailian Xiao A novel and efficient catalyst system was developed for homocoupling reactions of aryl halides. The catalyst system consists of Pd(OAc)₂ and the peppery sensory component of tobacco leaves. This is the first time that a sensory component has been used in an organic reaction. Experiments using the catalyst system showed that the reactions proceeded smoothly under air in the absence of both an additional ligand and a reductant. Furthermore, the catalyst system can be applied to the coupling reactions of hetaryl iodides. Many functional groups (including a hydroxy group) are tolerated.