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

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Title: Room temperature catalytic carbon-hydrogen bond alumination of unactivated arenes: mechanism and selectivity
Authors: Hooper, TN
Garcon, M
White, AJP
Crimmin, MR
Item Type: Journal Article
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.
Issue Date: 28-Jun-2018
Date of Acceptance: 28-May-2018
URI: http://hdl.handle.net/10044/1/61112
DOI: https://dx.doi.org/10.1039/c8sc02072h
ISSN: 2041-6520
Publisher: Royal Society of Chemistry
Start Page: 5435
End Page: 5440
Journal / Book Title: CHEMICAL SCIENCE
Volume: 9
Issue: 24
Copyright Statement: © 2018 The Royal Society of Chemistry. Open Access. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (https://creativecommons.org/licenses/by/3.0/).
Sponsor/Funder: The Royal Society
Commission of the European Communities
Funder's Grant Number: UF090149
677367
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
C-H BORYLATION
TRANS ISOMERIZATION
AROMATIC BORYLATION
OXIDATIVE ADDITION
ACTIVATION
COMPLEXES
LIGAND
ALUMINUM
CHEMISTRY
AL
Publication Status: Published
Open Access location: http://pubs.rsc.org/en/content/articlelanding/2018/sc/c8sc02072h#!divAbstract
Online Publication Date: 2018-05-29
Appears in Collections:Chemistry



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