6533b7d3fe1ef96bd12608e2

RESEARCH PRODUCT

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

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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.