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Issue 24, 2018
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Room temperature catalytic carbon–hydrogen bond alumination of unactivated arenes: mechanism and selectivity

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Abstract

We report the first catalytic methods for the transformation of C–H bonds of unactivated arenes into C–Al bonds. The catalytic reactions occur at 25 °C (benzene, toluene and xylenes) with palladium loadings as low as 0.1 mol%. Remarkably, the C–H activation of toluene and xylenes proceeds with ortho- and meta-selectivity. This selectivity is highly unusual and complementary to both Friedel–Crafts and the majority of C–H borylation methods. Through a detailed mechanistic analysis (Eyring analysis, KIE, DFT, QTAIM) we show that unusual Pd–Al intermetallic complexes are on the catalytic cycle and that the selectivity is determined by weak attractive dispersion forces in the transition state for C–H bond breaking.

Graphical abstract: Room temperature catalytic carbon–hydrogen bond alumination of unactivated arenes: mechanism and selectivity

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Publication details

The article was received on 09 May 2018, accepted on 28 May 2018 and first published on 29 May 2018


Article type: Edge Article
DOI: 10.1039/C8SC02072H
Citation: Chem. Sci., 2018,9, 5435-5440
  • Open access: Creative Commons BY license
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    Room temperature catalytic carbon–hydrogen bond alumination of unactivated arenes: mechanism and selectivity

    T. N. Hooper, M. Garçon, A. J. P. White and M. R. Crimmin, Chem. Sci., 2018, 9, 5435
    DOI: 10.1039/C8SC02072H

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