The Effect of β‐Hydrogen Atoms on Iron Speciation in Cross‐Couplings with Simple Iron Salts and Alkyl Grignard Reagents
Open accessAbstract
The effects of β‐hydrogen‐containing alkyl Grignard reagents in simple ferric salt cross‐couplings have been elucidated. The reaction of FeCl 3 with EtMgBr in THF leads to the formation of the cluster species [Fe 8 Et 12 ] 2− , a rare example of a structurally characterized metal complex with bridging ethyl ligands. Analogous reactions in the presence of NMP, a key additive for effective cross‐coupling with simple ferric salts and β‐hydrogen‐containing alkyl nucleophiles, result in the formation of [FeEt 3 ] − . Reactivity studies demonstrate the effectiveness of [FeEt 3 ] − in rapidly and selectively forming the cross‐coupled product upon reaction with electrophiles. The identification of iron‐ate species with EtMgBr analogous to those previously observed with MeMgBr is a critical insight, indicating that analogous iron species can be operative in catalysis for these two classes of alkyl nucleophiles.
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Addition of N-methyl pyrrolidone (NMP), a cyclic tertiary amide, has been shown to enhance the catalytic activity of iron in cross-coupling reactions which enables the formation of catalytically active monomeric ferrates by coordination.
“In fact, the addition of N-methyl pyrrolidone (NMP), a cyclic tertiary amide, has been shown to enhance the catalytic activity of iron in cross-coupling reactions which enables the formation of catalytically active monomeric ferrates by coordination.70–73”
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References 28 · Cited by 50
Research works printed but not linked: 5
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- Authors
- Sears, J. D., Muñoz, S. B., Daifuku, S. L., Shaps, A. A., Carpenter, S. H., Brennessel, W. W., & Neidig, M. L.
- Affiliations
- University of Rochester (US)
- Corresponding author
- Neidig, Michael L.
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2019-01-29
- Volume
- 58
- Issue
- 9
- Pages
- 2769-2773
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- PMC
- PMC6472485
- OpenAlex
- W2908591097
- Cited by
- 50
- References
- 28
- Citations by year
- 2026: 2 · 2025: 1 · 2024: 6 · 2023: 3 · 2022: 8 · 2021: 11 · 2020: 15 · 2019: 4
- FWCI
- 3.73
- Type
- journal article
- Language
- en
- Open access
- green
- www.ncbi.nlm.nih.gov
- Licence
- Locations
- Angewandte Chemie International Edition (publishedVersion)
- PubMed (publishedVersion)
- PubMed Central (acceptedVersion)
- Funders
- National Institute of General Medical Sciences (R01GM111480, F32GM120823)
- Division of Chemistry (CHE-1725028)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Catalytic Cross-Coupling Reactions
- Physical Sciences › Chemistry › Organic Chemistry › Coordination Chemistry and Organometallics
- Physical Sciences › Chemistry › Organic Chemistry › Inorganic and Organometallic Chemistry
- Keywords
- iron speciation, ferric chloride, ethylmagnesium bromide, iron catalysis
- MeSH terms
- Ferric Compounds, Hydrogen, Models, Molecular, Organometallic Compounds, Salts, Molecular Structure, Crystallography, X-Ray
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