Issue 95, 2021

Intermediates and mechanism in iron-catalyzed C–H methylation with trimethylaluminum

Abstract

A mechanistic study is performed on the reaction method for iron-catalyzed C–H methylation with AlMe3 reagent, previously proposed to involve cyclometalated iron(III) intermediates and an iron(III)/(I) reaction cycle. Detailed spectroscopic studies (57Fe Mössbauer, EPR) during catalysis and in stoichiometric reactions identify iron(II) complexes, including cyclometalated iron(II) intermediates, as the major iron species formed in situ under catalytic reaction conditions. Reaction studies identify a cyclometalated iron(II)-methyl species as the key intermediate leading to C–H methylated product upon reaction with oxidant, consistent with a previously proposed iron(II)/iron(III)/iron(I) reaction manifold for C–H arylation.

Graphical abstract: Intermediates and mechanism in iron-catalyzed C–H methylation with trimethylaluminum

Supplementary files

Article information

Article type
Communication
Submitted
04 oct. 2021
Accepted
29 oct. 2021
First published
16 nov. 2021

Chem. Commun., 2021,57, 12784-12787

Author version available

Intermediates and mechanism in iron-catalyzed C–H methylation with trimethylaluminum

S. Bhatia, J. C. DeMuth and M. L. Neidig, Chem. Commun., 2021, 57, 12784 DOI: 10.1039/D1CC05607G

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