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@unpublished{Brown:2021:10.26434/chemrxiv.14662932.v1,
author = {Brown, R and hooper, TN and Rekroukh, F and White, AJP and Costa, PJ and Crimmin, M},
doi = {10.26434/chemrxiv.14662932.v1},
title = {Alumination of Aryl Methyl Ethers: Switching Between Sp2 and Sp3 C–O Bond Functionalisation with Pd-Catalysis},
url = {http://dx.doi.org/10.26434/chemrxiv.14662932.v1},
year = {2021}
}

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TY  - UNPB
AB  - <jats:p>The reaction of [{(ArNCMe)2CH}Al] (Ar = 2,6-di-iso-propylphenyl, 1) with aryl methyl ethers proceeded with alumination of the sp3 C–O bond by a presumed SN2 pathway. The selectivity of this reaction could be switched by inclusion of a catalyst. In the presence of [Pd(PCy3)2], chemoselective sp2 C–O bond functionalisation was observed. Kinetic isotope experiments and DFT calculations support a catalytic pathway involving the ligand-assisted oxidative addition of the sp2 C–O bond to a Pd---Al intermetallic complex. The net result of both non-catalysed and catalytic pathways is the generation of polar organoaluminium complexes from aryl methyl ethers with complete atom-efficiency. Switches in selectivity yield isomeric products from a single starting material. The methodology (and mechanistic insight) holds promise as a means to functionalise aromatic molecules derived from lignin depolymerisation and we demonstrate an application to a derivative of vanillin.</jats:p>
AU  - Brown,R
AU  - hooper,TN
AU  - Rekroukh,F
AU  - White,AJP
AU  - Costa,PJ
AU  - Crimmin,M
DO  - 10.26434/chemrxiv.14662932.v1
PY  - 2021///
TI  - Alumination of Aryl Methyl Ethers: Switching Between Sp2 and Sp3 C–O Bond Functionalisation with Pd-Catalysis
UR  - http://dx.doi.org/10.26434/chemrxiv.14662932.v1
ER  -

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Professor Mark R. Crimmin

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