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Issue 7, 2018

NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling

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Abstract

While iron–NHC catalysed cross-couplings have been shown to be effective for a wide variety of reactions (e.g. aryl–aryl, aryl–alkyl, alkyl–alkyl), the nature of the in situ formed and reactive iron species in effective catalytic systems remains largely undefined. In the current study, freeze-trapped Mössbauer spectroscopy, and EPR studies combined with inorganic synthesis and reaction studies are utilised to define the key in situ formed and reactive iron–NHC species in the Kumada alkyl–alkyl cross-coupling of (2-(1,3-dioxan-2-yl)ethyl)magnesium bromide and 1-iodo-3-phenylpropane. The key reactive iron species formed in situ is identified as (IMes)Fe((1,3-dioxan-2-yl)ethyl)2, whereas the S = 1/2 iron species previously identified in this chemistry is found to be only a very minor off-cycle species (<0.5% of all iron). Reaction and kinetic studies demonstrate that (IMes)Fe((1,3-dioxan-2-yl)ethyl)2 is highly reactive towards the electrophile resulting in two turnovers with respect to iron (kobs > 24 min−1) to generate cross-coupled product with overall selectivity analogous to catalysis. The high resistance of this catalytic system to β-hydride elimination of the alkyl nucleophile is attributed to its chelation to iron through ligation of carbon and one oxygen of the acetal moiety of the nucleophile. In fact, alternative NHC ligands such as SIPr are less effective in catalysis due to their increased steric bulk inhibiting the ability of the alkyl ligands to chelate. Overall, this study identifies a novel alkyl chelation method to achieve effective alkyl–alkyl cross-coupling with iron(II)–NHCs, provides direct structural insight into NHC effects on catalytic performance and extends the importance of iron(II) reactive species in iron-catalysed cross-coupling.

Graphical abstract: NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling

Supplementary files

Article information


Submitted
02 Nov 2017
Accepted
02 Jan 2018
First published
08 Jan 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 1878-1891
Article type
Edge Article

NHC and nucleophile chelation effects on reactive iron(II) species in alkyl–alkyl cross-coupling

V. E. Fleischauer, S. B. Muñoz III, P. G. N. Neate, W. W. Brennessel and M. L. Neidig, Chem. Sci., 2018, 9, 1878 DOI: 10.1039/C7SC04750A

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