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Relevance of Single-Transmetalated Resting States in Iron-Mediated Cross-Couplings: Unexpected Role of σ-Donating Additives

Abstract : Control of the transmetalation degree of organoiron(II) species is a critical parameter in numerous Fe-catalyzed cross-couplings to ensure the success of the process. In this report, we however demonstrate that the selective formation of a monotransmetalated FeII species during the catalytic regime counterintuitively does not alone ensure an efficient suppression of the nucleophile homocoupling side reaction. It is conversely shown that a fine control of the transmetalation degree of the transient FeIII intermediates obtained after the activation of alkyl electrophiles by a single-electron transfer (SET), achievable using σ-donating additives, accounts for the selectivity of the cross-coupling pathway. This report shows for the first time that both coordination spheres of FeII resting states and FeIII short-lived intermediates must be efficiently tuned during the catalytic regime to ensure high coupling selectivities.
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https://hal-cea.archives-ouvertes.fr/cea-03228273
Contributor : Serge Palacin <>
Submitted on : Tuesday, May 18, 2021 - 7:54:02 AM
Last modification on : Tuesday, June 8, 2021 - 11:53:12 AM

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Lidie Rousseau, Nadia Touati, Laurent Binet, Pierre Thuéry, Guillaume Lefèvre. Relevance of Single-Transmetalated Resting States in Iron-Mediated Cross-Couplings: Unexpected Role of σ-Donating Additives. Inorganic Chemistry, American Chemical Society, In press, 60 (11), pp.7991-7997. ⟨10.1021/acs.inorgchem.1c00518⟩. ⟨cea-03228273⟩

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