A1 Journal article (refereed)
Arene C‐H activation at aluminium(I) : meta selectivity driven by the electronics of SNAr chemistry (2020)


Hicks, Jamie; Vasko, Petra; Heilmann, Andreas; Goicoechea, Jose; Aldridge, Simon (2020). Arene C‐H activation at aluminium(I) : meta selectivity driven by the electronics of SNAr chemistry. Angewandte Chemie, Early online. DOI: 10.1002/anie.202008557


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Publication details

All authors or editors: Hicks, Jamie; Vasko, Petra; Heilmann, Andreas; Goicoechea, Jose; Aldridge, Simon

Journal or series: Angewandte Chemie

ISSN: 1433-7851

eISSN: 1521-3773

Publication year: 2020

Volume: Early online

Publisher: Wiley

Publication country: Germany

Publication language: English

DOI: http://doi.org/10.1002/anie.202008557

Open Access: Publication channel is not openly available

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/71279


Abstract

The reactivity of the electron-rich anionic Al(I) (‘aluminyl’) compound K 2 [(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 S N Ar chemistry, which implies the destabilization of transition states featuring electron-donating groups in either the ortho or the 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 or para to a methyl substituent.


Keywords: aluminium

Free keywords: aluminium; aluminyl nucleophile; C-H activation; arenes; SNAr mechanism


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Last updated on 2020-30-07 at 09:10