Arene C−H Activation at Aluminium(I): meta Selectivity Driven by the Electronics of SNAr Chemistry

Jamie Hicks, Petra Vasko, Andreas Heilmann, Jose M. Goicoechea*, Simon Aldridge*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    43 Citations (Scopus)

    Abstract

    The 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.

    Original languageEnglish
    Pages (from-to)20376-20380
    Number of pages5
    JournalAngewandte Chemie - International Edition
    Volume59
    Issue number46
    DOIs
    Publication statusPublished - 9 Nov 2020

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