Hicks, JamieVasko, PetraHeilmann, AndreasGoicoechea, Jose MAldridge, Simon2022-07-202022-07-201433-7851http://hdl.handle.net/1885/269817The reactivity of the electron‐rich anionic AlI aluminyl compound K2[(NON)Al]2 (NON=4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) towards mono‐ and disubstituted arenes is reported. C−H activation chemistry with n‐butylbenzene gives exclusively the product of activation at the arene meta position. Mechanistically, this transformation proceeds in a single step via a concerted Meisenheimer‐type transition state. Selectivity is therefore based on similar electronic factors to classical SNAr chemistry, which implies the destabilisation of transition states featuring electron‐donating groups in either ortho or para positions. In the cases of toluene and the three isomers of xylene, benzylic C−H activation is also possible, with the product(s) formed reflecting the feasibility (or otherwise) of competing arene C−H activation at a site which is neither ortho nor para to a methyl substituent.P.V. thanks the Academy of Finland (Grant No. 314794) and Prof. Heikki Tuononen for providing computational resources. J.H. thanks the Australian Research Council for funding (DE190100524).application/pdfen-AU© 2020 The Authors. Published by Wiley-VCH GmbH202010.1002/anie.2020085572021-08-01Creative Commons Attribution License