A1 Journal article (refereed)
Arene C‐H activation at aluminium(I) : meta selectivity driven by the electronics of SNAr chemistry (2020)
Hicks, J., Vasko, P., Heilmann, A., Goicoechea, J., & Aldridge, S. (2020). Arene C‐H activation at aluminium(I) : meta selectivity driven by the electronics of SNAr chemistry. Angewandte Chemie, 59(46), 20376-20380. https://doi.org/10.1002/anie.202008557
JYU authors or editors
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: 59
Issue number: 46
Pages range: 20376-20380
Publisher: Wiley
Publication country: Germany
Publication language: English
DOI: https://doi.org/10.1002/anie.202008557
Publication open access: Openly available
Publication channel open access: Partially open access channel
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
Contributing organizations
Related projects
- Low-valent Main Group/Transition Metal Hetero-bimetallic complexes for Small Molecule Activation
and Catalysis- Vasko, Petra
- Research Council of Finland
Ministry reporting: Yes
Reporting Year: 2020
JUFO rating: 3