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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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Supplementary files

Article information


Submitted
09 May 2018
Accepted
28 May 2018
First published
29 May 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 5435-5440
Article type
Edge Article

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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