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NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling
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-trappe...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5890793/ https://www.ncbi.nlm.nih.gov/pubmed/29675234 http://dx.doi.org/10.1039/c7sc04750a |
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author | Fleischauer, Valerie E. Muñoz III, Salvador B. Neate, Peter G. N. Brennessel, William W. Neidig, Michael L. |
author_facet | Fleischauer, Valerie E. Muñoz III, Salvador B. Neate, Peter G. N. Brennessel, William W. Neidig, Michael L. |
author_sort | Fleischauer, Valerie E. |
collection | PubMed |
description | 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 (k(obs) > 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. |
format | Online Article Text |
id | pubmed-5890793 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-58907932018-04-19 NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling Fleischauer, Valerie E. Muñoz III, Salvador B. Neate, Peter G. N. Brennessel, William W. Neidig, Michael L. Chem Sci Chemistry 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 (k(obs) > 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. Royal Society of Chemistry 2018-01-08 /pmc/articles/PMC5890793/ /pubmed/29675234 http://dx.doi.org/10.1039/c7sc04750a Text en This journal is © The Royal Society of Chemistry 2018 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry Fleischauer, Valerie E. Muñoz III, Salvador B. Neate, Peter G. N. Brennessel, William W. Neidig, Michael L. NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling |
title | NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling
|
title_full | NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling
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title_fullStr | NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling
|
title_full_unstemmed | NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling
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title_short | NHC and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling
|
title_sort | nhc and nucleophile chelation effects on reactive iron(ii) species in alkyl–alkyl cross-coupling |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5890793/ https://www.ncbi.nlm.nih.gov/pubmed/29675234 http://dx.doi.org/10.1039/c7sc04750a |
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