Room temperature catalytic carbon-hydrogen bond alumination of unactivated arenes: mechanism and selectivity

Chemical Science
Thomas N HooperMark R Crimmin

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.

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Citations

Oct 16, 2018·Chemical Communications : Chem Comm·Martí GarçonMark R Crimmin
Aug 30, 2019·Angewandte Chemie·Steffen BrandSjoerd Harder
Jan 17, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Mingdong ZhongHerbert W Roesky
Feb 14, 2020·Chemistry : a European Journal·Kengo Sugita, Makoto Yamashita
Feb 9, 2020·Chemistry : a European Journal·Uddhav Kanbur, Aaron David Sadow
May 22, 2020·Angewandte Chemie·Anton DmitrienkoGeorgii I Nikonov
Jun 23, 2020·Angewandte Chemie·Jamie HicksSimon Aldridge
Nov 26, 2019·Chemical Science·Thomas N HooperMark R Crimmin
Dec 4, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Marcella E Desat, Robert Kretschmer
Mar 19, 2019·Chemical Science·Clare BakewellMark R Crimmin
May 19, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Richard Y Kong, Mark R Crimmin
May 27, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Maximilian DehmelRobert Kretschmer
Jun 3, 2021·Chemical Communications : Chem Comm·Weixing ChenXiao-Juan Yang
Jun 8, 2021·Chemical Science·Thomas N HooperMark R Crimmin
Jun 25, 2021·Chemical Science·Maria BatuecasMark R Crimmin
Jun 15, 2021·Chemical Science·Katie HobsonClare Bakewell
Jul 25, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·José Manuel Guevara-VelaÁngel Martín Pendás
Aug 15, 2019·Inorganic Chemistry·Rosalyn L FalconerMichael J Cowley
Sep 9, 2020·Inorganic Chemistry·Johannes KretschDietmar Stalke
Aug 17, 2021·Angewandte Chemie·Matthew M D RoySimon Aldridge

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Methods Mentioned

BETA
X-ray
neutron diffraction

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